CN110993962B - Heteropolyacid/reduced graphene oxide/polypyrrole composite material and preparation method and application thereof - Google Patents
Heteropolyacid/reduced graphene oxide/polypyrrole composite material and preparation method and application thereof Download PDFInfo
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- CN110993962B CN110993962B CN201911166238.0A CN201911166238A CN110993962B CN 110993962 B CN110993962 B CN 110993962B CN 201911166238 A CN201911166238 A CN 201911166238A CN 110993962 B CN110993962 B CN 110993962B
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- H01M8/00—Fuel cells; Manufacture thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H—ELECTRICITY
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- H01M4/90—Selection of catalytic material
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Abstract
The invention relates to the technical field of microbial fuel cells, and particularly discloses a heteropoly acid/reduced graphene oxide/polypyrrole composite material and a preparation method and application thereof. The preparation method comprises the following steps: mixing the graphene oxide turbid liquid with a heteropoly acid solution, adding isopropanol, and carrying out photocatalytic reaction to obtain a heteropoly acid/reduced graphene oxide turbid liquid; and mixing the pyrrole prepolymerization solution with the heteropoly acid/reduced graphene oxide turbid liquid, and stirring for reaction to obtain the heteropoly acid/reduced graphene oxide/polypyrrole composite material turbid liquid. The preparation method provided by the invention has the advantages of simple process, convenience in operation, low energy consumption, low cost, safety and environmental friendliness, and the obtained composite material has high specific surface area, high biocatalysis performance, high conductivity and good biocompatibility, and can improve the electricity generation performance and perchlorate removal performance of the microbial fuel cell.
Description
Technical Field
The invention relates to the technical field of microbial fuel cells, in particular to a heteropoly acid/reduced graphene oxide/polypyrrole composite material and a preparation method and application thereof.
Background
At present, under the double pressure of environmental pollution and energy shortage, the appearance of Microbial Fuel Cell (MFC) technology provides a new idea for solving the two problems. The microbial fuel cell has the unique advantages of high efficiency, cleanness and environmental protection, and is regarded by people and becomes a research hotspot in the environmental field. The microbial fuel cell is a device which directly converts chemical energy in organic matters into electric energy by using microbes, and generates the electric energy while removing pollutants.
However, the microbial fuel cell technology still has the problems of low output voltage, difficult mass production and the like. The anode of the microbial fuel cell is used as an important carrier for attaching electrogenic microorganisms, and directly influences the enrichment growth, substrate oxidation and electron transfer of electrogenic bacteria, so that the selection of a high-efficiency anode material plays a decisive role in improving the electrogenic capability of the microbial fuel cell.
Disclosure of Invention
Aiming at the technical problems in the prior MFC technology, the invention provides a heteropoly acid/reduced graphene oxide/polypyrrole composite material, and a preparation method and application thereof.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a preparation method of a heteropoly acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing graphene oxide in deionized water to prepare a graphene oxide turbid liquid; dissolving heteropoly acid in deionized water to prepare heteropoly acid solution; adding pyrrole into an oxidant solution to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with the heteropoly acid solution, adding isopropanol, and performing photocatalytic reaction to obtain heteropoly acid/reduced graphene oxide turbid liquid;
s3: and mixing the pyrrole prepolymerization solution with the heteropoly acid/reduced graphene oxide turbid liquid, and stirring for reaction to obtain the heteropoly acid/reduced graphene oxide/polypyrrole composite material turbid liquid.
Compared with the prior art, the preparation method of the heteropoly acid/reduced graphene oxide/polypyrrole composite material provided by the invention has the advantages that heteropoly acid and Graphene Oxide (GO) are used as raw materials, a photocatalytic reaction is carried out in the presence of isopropanol, the heteropoly acid is reduced into heteropoly blue after being subjected to photocatalysis, oxidized graphene is oxidized into oxidation state heteropoly acid, and the graphene oxide is reduced into reduced graphene oxide (rGO), and the heteropoly acid and the reduced graphene oxide have strong attraction due to the interaction of electron transfer and static electricity, and are combined to form a heteropoly acid/reduced graphene oxide composite; and after the heteropoly acid/reduced graphene oxide is mixed with the pyrrole prepolymerization solution, pyrrole reacts to form polypyrrole (PPy) and is simultaneously compounded with the heteropoly acid/reduced graphene oxide, and the heteropoly acid/reduced graphene oxide/polypyrrole composite material is formed through electrostatic interaction because the reduced graphene oxide is negatively charged and the polypyrrole is positively charged. The preparation method has the advantages of simple process, convenient operation, low energy consumption, low cost, safety and environmental protection.
Further, the heteropoly acid is phosphomolybdic acid (PMo)12) Or phosphotungstic acid (PW)12) The graphene oxide catalyst has better oxidation-reduction catalytic performance and is more favorable for reacting with graphene oxide to form a compound.
Further, the dosage ratio of the graphene oxide to the heteropoly acid to the pyrrole is 0.10-0.30 g: 1.00-3.00 g: 1.00-3.00 mL, the heteropolyacid has good electrocatalytic performance, but is easy to aggregate in water, so that the specific surface area of the heteropolyacid is reduced; the reduced graphene oxide has large specific surface area and good conductivity, but has certain toxicity to microorganisms, so that the performance of the composite material is improved by compounding heteropoly acid, reduced graphene oxide and polypyrrole, the heteropoly acid is dispersed and fixed on the reduced graphene oxide by controlling the using amount of each component, the aggregation of the heteropoly acid is prevented, the specific surface area of the heteropoly acid is improved, and then the heteropoly acid is combined with the polypyrrole to improve the conductivity of the composite material, reduce the toxicity of the reduced graphene oxide to the microorganisms, and improve the biocompatibility of the composite material, so that the heteropoly acid/reduced graphene oxide/polypyrrole composite material with high specific surface area, high catalytic activity, high conductivity and good biocompatibility is obtained. The dosage ratio of the heteropoly acid to the isopropanol is 1.00-3.00 g: and adding sufficient isopropanol into the mixture of 30-90 mu L, wherein the isopropanol can react with hydroxyl radicals generated in the reaction process, so that the reduction of heteropoly acid by the hydroxyl radicals is avoided, the electron reduced heteropoly acid in an excited state is heteropolyblue, and the subsequent reaction with graphene oxide is facilitated.
Further, the ratio of the amount of pyrrole to the amount of oxidant substance is 3 to 15: 1-3, ensuring that pyrrole monomers are fully reacted into polypyrrole, wherein the oxidant is ammonium persulfate.
Further, the mass concentration of the heteropoly acid solution is 16.00-50.00 mg/mL-1(ii) a The mass concentration of the graphene oxide turbid liquid is 1.00-3.00 mg/mL-1(ii) a The mass concentration of the oxidant solution is 45-137 mg/mL-1。
Further, the time of the photocatalytic reaction is 8-12 hours, so that the sufficient reaction is ensured, and a heteropoly acid/reduced graphene oxide suspension is formed; in the step S3, the reaction temperature is 30-40 ℃, the reaction time is 5-7 hours, the reduced graphene oxide is ensured to be fully contacted with polypyrrole, and the composite material is formed through electrostatic interaction.
The invention also provides a heteropoly acid/reduced graphene oxide/polypyrrole composite material prepared by the preparation method. The obtained composite material uses reduced graphene oxide as a carrier to load heteropoly acid, and the heteropoly acid is highly dispersed on the surface of the reduced graphene oxide, so that the specific surface area of the composite material is increased; and the composite material is combined with polypyrrole to effectively improve the conductivity of the composite material, so that the composite material has high specific surface area, high biocatalysis performance, high conductivity and good biocompatibility.
The invention also provides application of the heteropoly acid/reduced graphene oxide/polypyrrole composite material in a microbial fuel cell.
The invention also provides a microbial fuel cell anode material which comprises a base material and the heteropoly acid/reduced graphene oxide/polypyrrole composite material deposited on the base material.
The invention also provides a preparation method of the anode material, which comprises the following steps: and (3) depositing the composite material on the surface of a base material by adopting a cyclic voltammetry, and washing and drying to obtain the anode material of the microbial fuel cell.
Further, the substrate is a carbon-based material, specifically, the carbon-based material is carbon cloth, the potential of the cyclic voltammetry is-1.50-0.50V, and the sweep rate is 40-60 mV · s-1The number of scanning turns is 30-50 turns.
The heteropoly acid/reduced graphene oxide/polypyrrole composite material provided by the invention modifies a carbon-based material to form a microbial fuel cell anode material, so that the growth environment of bacteria on the surface of an electrode is improved, and because polypyrrole is positively charged and has good conductivity and biocompatibility, negatively charged bacteria can be attracted to be attached to the surface of the electrode to form a biological membrane, the attachment amount of microorganisms is increased, and the electron transfer between the electrogenic microorganisms and the electrode is facilitated, so that the electrogenic performance and the pollutant removal performance of MFC are improved.
Drawings
FIG. 1 is a blank anode SEM image;
FIG. 2 shows an embodiment PMo of the present invention12SEM image of/rGO/PPy anode;
FIG. 3 is a non-photocatalytic PMo of a comparative example of the present invention12SEM image of/rGO/PPy anode;
FIG. 4 shows a flowchart of an embodiment PW of the present invention12SEM image of/rGO/PPy anode;
FIG. 5 shows a non-photocatalytic PW according to a comparative example of the present invention12SEM image of/rGO/PPy anode;
FIG. 6 is a graph of the power generation performance of MFCs corresponding to different anodes;
fig. 7 is a graph of perchlorate removal rates of MFC for different anodes.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.20g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; dissolving 2.00g of phosphomolybdic acid in 60mL of deionized water to prepare a phosphomolybdic acid solution; dissolving 2.28g (10.00mmol) of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 2mL (30.00mmol) of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with a phosphomolybdic acid solution, adding 60 mu L of isopropanol, and reacting in a photocatalytic reactor for 10 hours to obtain phosphomolybdic acid/reduced graphene oxide turbid liquid;
s3: and mixing the pyrrole prepolymerization solution with a phosphomolybdic acid/reduced graphene oxide turbid liquid, and stirring and reacting for 6 hours at 35 ℃ to obtain a turbid liquid of a phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material.
The phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material is applied to the preparation of the anode material of the microbial fuel cell, and the preparation method of the anode material comprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in turbid liquid of phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry method; the sweeping speed is 50mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) performing electro-deposition on the composite material on the surface of the carbon cloth with the number of scanning turns of 40 turns, washing the carbon cloth with deionized water, and drying the carbon cloth at room temperature to obtain the carbon cloth with the surface modified by phosphomolybdic acid/reduced graphene oxide/polypyrrole, namely the MFC anode material.
Example 2
A preparation method of phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.10g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; dissolving 1.00g of phosphomolybdic acid in 60mL of deionized water to prepare a phosphomolybdic acid solution; dissolving 3.42g (15.00mmol) of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 3mL (45.00mmol) of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with a phosphomolybdic acid solution, adding 90 mu L of isopropanol, and reacting in a photocatalytic reactor for 8 hours to obtain phosphomolybdic acid/reduced graphene oxide turbid liquid;
s3: and mixing the pyrrole prepolymerization solution with a phosphomolybdic acid/reduced graphene oxide turbid liquid, and stirring and reacting for 7 hours at the temperature of 30 ℃ to obtain a turbid liquid of a phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material.
The phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material is applied to the preparation of the anode material of the microbial fuel cell, and the preparation method of the anode material comprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in turbid liquid of a phosphomolybdic acid/graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry; the sweeping speed is 60mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) scanning for 50 circles, electrodepositing the composite material on the surface of the carbon cloth, washing with deionized water, and airing at room temperature to obtain the carbon cloth with the surface modified by phosphomolybdic acid/graphene oxide/polypyrrole, namely the MFC anode material.
Example 3
A preparation method of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.20g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; 2.00g of phosphotungstic acid is dissolved in 60mL of deionized water to prepare a phosphotungstic acid solution; dissolving 2.28g (10.00mmol) of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 2mL (30.00mmol) of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with a phosphotungstic acid solution, adding 60 mu L of isopropanol, and reacting in a photocatalytic reactor for 10 hours to obtain a phosphotungstic acid/reduced graphene oxide turbid liquid;
s3: and mixing the pyrrole prepolymerization solution with a phosphotungstic acid/reduced graphene oxide turbid liquid, and stirring and reacting for 6 hours at 35 ℃ to prepare a turbid liquid of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material.
The application of the phosphotungstic acid/reduced graphene oxide/polypyrrole composite material in the microbial fuel cell is used for preparing an anode material of the microbial fuel cell, and the preparation method of the anode material comprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in suspension of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry; the sweeping speed is 50mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) performing electro-deposition on the composite material on the surface of the carbon cloth with the number of scanning turns of 40 turns, washing the carbon cloth with deionized water, and drying the carbon cloth at room temperature to obtain the carbon cloth with the surface modified by phosphotungstic acid/reduced graphene oxide/polypyrrole, namely the MFC anode material.
Example 4
A preparation method of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.30g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; dissolving 3.00g of phosphotungstic acid in 60mL of deionized water to prepare a phosphotungstic acid solution; dissolving 1.14g (5.00mmol) of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 1mL (15.00mmol) of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide suspension with a phosphotungstic acid solution, adding 30 mu L of isopropanol, and reacting in a photocatalytic reactor for 12 hours to obtain a phosphotungstic acid/reduced graphene oxide suspension;
s3: and mixing the pyrrole prepolymerization solution with a phosphotungstic acid/reduced graphene oxide turbid liquid, and stirring and reacting for 5 hours at 40 ℃ to prepare a turbid liquid of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material.
The application of the phosphotungstic acid/reduced graphene oxide/polypyrrole composite material in the microbial fuel cell is used for preparing an anode material of the microbial fuel cell, and the preparation method of the anode material comprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in suspension of a phosphotungstic acid/reduced graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry; the sweeping speed is 40mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) performing electro-deposition on the composite material on the surface of the carbon cloth with the number of scanning turns of 30 turns, washing the carbon cloth with deionized water, and drying the carbon cloth at room temperature to obtain the carbon cloth with the surface modified by phosphotungstic acid/reduced graphene oxide/polypyrrole, namely the MFC anode material.
In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.
Comparative example 1
A preparation method of a non-photocatalytic phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.20g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; dissolving 2.00g of phosphomolybdic acid in 60mL of deionized water to prepare a phosphomolybdic acid solution; dissolving 2.28g of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 2mL of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with a phosphomolybdic acid solution, and reacting at room temperature for 10 hours to obtain non-photocatalytic phosphomolybdic acid/reduced graphene oxide turbid liquid;
s3: and mixing the pyrrole prepolymerization solution with the suspension of non-photocatalytic phosphomolybdic acid/reduced graphene oxide, and stirring and reacting at 35 ℃ for 6 hours to obtain the suspension of the non-photocatalytic phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material.
The application of the non-photocatalytic phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material in the microbial fuel cell is used for preparing an anode material of the microbial fuel cell, and the preparation method of the anode material comprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in a suspension of a non-photocatalytic phosphomolybdic acid/reduced graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry; the sweeping speed is 50mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) performing electro-deposition on the composite material on the surface of the carbon cloth with the number of scanning turns of 40 turns, washing the carbon cloth with deionized water, and drying the carbon cloth at room temperature to obtain the carbon cloth with the surface which is not modified by photocatalytic phosphomolybdic acid/reduced graphene oxide/polypyrrole, namely the MFC anode material.
Comparative example 2
A preparation method of non-photocatalytic phosphotungstic acid/reduced graphene oxide/polypyrrole composite material comprises the following steps:
s1: dispersing 0.20g of graphene oxide in 100mL of deionized water, stirring and ultrasonically dispersing for 90min to prepare a graphene oxide suspension; 2.00g of phosphotungstic acid is dissolved in 60mL of deionized water to prepare a phosphotungstic acid solution; dissolving 2.28g of ammonium persulfate in 25mL of deionized water, stirring to prepare an ammonium persulfate solution, dropwise adding 2mL of pyrrole into the ammonium persulfate solution, stirring and reacting to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide suspension with a phosphotungstic acid solution, and reacting at room temperature for 10 hours to obtain a non-photocatalytic phosphotungstic acid/reduced graphene oxide suspension;
s3: and mixing the pyrrole prepolymerization solution with the non-photocatalytic phosphotungstic acid/reduced graphene oxide turbid liquid, and stirring and reacting for 6 hours at 35 ℃ to prepare the non-photocatalytic phosphotungstic acid/reduced graphene oxide/polypyrrole composite turbid liquid.
The application of the non-photocatalytic phosphotungstic acid/reduced graphene oxide/polypyrrole composite material in the microbial fuel cell, the preparation of the anode material of the microbial fuel cell and the preparation method of the anode materialComprises the following steps: the method comprises the following steps of (1) adopting a three-electrode system, taking carbon cloth pretreated by nitric acid as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, placing the three electrodes in a suspension of a non-photocatalytic phosphotungstic acid/reduced graphene oxide/polypyrrole composite material, and setting the potential to be-1.50-0.50V by adopting a cyclic voltammetry; the sweeping speed is 50mV s-1(ii) a Sensitivity of 10-3(ii) a And (3) performing electro-deposition on the composite material on the surface of the carbon cloth with the number of scanning turns of 40 turns, washing the carbon cloth with deionized water, and drying the carbon cloth at room temperature to obtain the carbon cloth with the surface which is not modified by the photocatalytic phosphotungstic acid/reduced graphene oxide/polypyrrole, namely the MFC anode material.
To better illustrate the characteristics of the heteropoly acid/reduced graphene oxide/polypyrrole composite material provided by the embodiments of the present invention, the MFC anode material (PMo) prepared in example 1 is described below12/rGO/PPy anode), MFC anode material prepared in example 3 (PW)12/rGO/PPy anode), MFC anode material prepared in comparative example 1 (non-photocatalytic PMo)12/rGO/PPy anode), MFC anode material prepared in comparative example 2 (non-photocatalytic PW)12/rGO/PPy anode) and carbon cloth pretreated with nitric acid (blank anode) were subjected to SEM analysis. Blank anode, PMo12/rGO/PPy anode, non-photocatalytic PMo12/rGO/PPy anode, PW12/rGO/PPy anode and non-photocatalytic PW12SEM results for the/rGO/PPy anodes are shown in FIGS. 1, 2, 3, 4 and 5, respectively, where the unmodified blank anodes had clean and smooth surfaces and PMo12Laminated, granular and cauliflower-like substances are superposed on the surface of the/rGO/PPy anode; PW (pseudo wire)12Spherical substances are attached to the surfaces of the sheets and are agglomerated together on the surface of the/rGO/PPy anode, and the sheets are mutually overlapped; non-photocatalytic PMo12/rGO/PPy anode and non-photocatalytic PW12The surface of the/rGO/PPy anode is dispersedly distributed with scattered flaky and granular substances which are not uniformly distributed, and PMo proves that12/rGO/PPy and PW12The specific surface area of the anode is greatly improved after the/rGO/PPy is modified.
In addition, a blank anode, PMo12/rGO/PPy anode, non-photocatalytic PMo12/rGO/PPy anode, PW12/rGO/PPy anode and non-photocatalytic PW12the/rGO/PPy anode is used for the anode of a single-chamber air cathode MFC, microorganisms, growth liquid and pollutants are added for culture, and the output voltage of the microbial fuel cell (shown in figure 6) and the perchlorate removal rate (shown in figure 7) are detected. In ClO4 -The concentration is 420 mg.L-1From a blank anode, PMo12/rGO/PPy anode, PW12/rGO/PPy anode, non-photocatalytic PMo12/rGO/PPy anode and non-photocatalytic PW12The maximum voltages generated by the MFC formed by the/rGO/PPy anode are 74.47mV, 148.285mV, 165.855mV, 105.74mV and 112.78mV respectively; ClO of hollow anode MFC in 12h4 -The removal rate is 97.88% at most, PMo12ClO of/rGO/PPy anode MFC4 -The removal rate reaches 100 percent in the 9 th hour, and PW is adopted12ClO of/rGO/PPy anode MFC at 7h4 -The removal rate reaches 100 percent (because the acid catalytic performance and the oxidation reduction catalytic performance of phosphotungstic acid are superior to phosphomolybdic acid, the PW is12Electricity generation and ClO of/rGO/PPy anode MFC4 -More excellent removal performance) without photocatalytic PMo12ClO of/rGO/PPy anode MFC4 -The removal rate reaches 100 percent in the 11 th hour, and the PW is not subjected to photocatalysis12ClO of/rGO/PPy anode MFC4 -The removal rate reaches 100% in 10 h.
The data show that the anode modified by the composite material provided by the embodiment of the invention has effectively increased surface area, is beneficial to the attachment of microorganisms on the surface of the anode, and improves the electricity generation and ClO of MFC4 -The performance is removed. The heteropoly acid/reduced graphene oxide/polypyrrole composite material provided by other embodiments of the invention has equivalent performance and effect to those of embodiment 1 or 3.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a heteropoly acid/reduced graphene oxide/polypyrrole composite material is characterized by comprising the following steps: the method comprises the following steps:
s1: dispersing graphene oxide in deionized water to prepare a graphene oxide turbid liquid; dissolving heteropoly acid in deionized water to prepare heteropoly acid solution; adding pyrrole into an oxidant solution to prepare a pyrrole prepolymerization solution;
s2: mixing the graphene oxide turbid liquid with the heteropoly acid solution, adding isopropanol, and performing photocatalytic reaction to obtain heteropoly acid/reduced graphene oxide turbid liquid;
s3: mixing the pyrrole prepolymerization solution with the heteropoly acid/reduced graphene oxide turbid liquid, and stirring for reaction to prepare a turbid liquid of the heteropoly acid/reduced graphene oxide/polypyrrole composite material; the heteropoly acid is phosphomolybdic acid or phosphotungstic acid.
2. The method of preparing a heteropoly acid/reduced graphene oxide/polypyrrole composite material according to claim 1, wherein: the dosage ratio of the graphene oxide to the heteropoly acid to the pyrrole is 0.10-0.30 g: 1.00-3.00 g: 1.00-3.00 mL; the dosage ratio of the heteropoly acid to the isopropanol is 1.00-3.00 g: 30-90 mu L.
3. The method of preparing a heteropoly acid/reduced graphene oxide/polypyrrole composite material according to claim 1, wherein: the amount ratio of pyrrole to oxidant is 3-15: 1 to 3.
4. The method of claim 3, wherein the heteropoly acid/reduced graphene oxide/polypyrrole composite material is prepared by the following steps: the time of the photocatalytic reaction is 8-12 h; in the step S3, the reaction temperature is 30-40 ℃ and the reaction time is 5-7 h.
5. A heteropoly acid/reduced graphene oxide/polypyrrole composite material is characterized in that: prepared by the preparation method of any one of claims 1 to 4.
6. Use of the heteropoly acid/reduced graphene oxide/polypyrrole composite material according to claim 5 in a microbial fuel cell.
7. A microbial fuel cell anode material, characterized in that: comprising a substrate and the heteropoly acid/reduced graphene oxide/polypyrrole composite material of claim 5 deposited on the substrate.
8. The method for preparing an anode material for a microbial fuel cell according to claim 7, wherein: and (3) depositing the composite material on the surface of a base material by adopting a cyclic voltammetry, and washing and drying to obtain the anode material of the microbial fuel cell.
9. The method of preparing a microbial fuel cell anode material of claim 8, wherein: the substrate is a carbon-based material, the potential of cyclic voltammetry is-1.50-0.50V, and the sweep rate is 40-60 mV · s-1The number of scanning turns is 30-50 turns.
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