CN112331864A - Biological melanin/graphene composite material and preparation method and application thereof - Google Patents
Biological melanin/graphene composite material and preparation method and application thereof Download PDFInfo
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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
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a biological melanin/graphene composite material and a preparation method and application thereof. The preparation method comprises the following steps: 1) mixing biological melanin with N, N-dimethylacetamide and heating to obtain a biological melanin solution; 2) mixing and heating a biological melanin solution, carboxylated graphene and an acidic solution to obtain a first mixture; 3) carrying out microwave catalytic reaction on the first mixture to obtain a second mixture; 4) carrying out ultrasonic treatment on the second mixture to obtain a third mixture; 5) and centrifuging, washing and drying the third mixture to obtain the biological melanin/graphene nano composite material. The biological melanin/graphene nanocomposite is coated on one side of a load platform and dried to obtain a biological melanin/graphene modified electrode, and the biological melanin/graphene modified electrode is used as a cathode of a microbial fuel cell and applied to the microbial fuel cell, has high electricity generation efficiency and can stably run for a long time.
Description
Technical Field
The invention belongs to the technical field of new energy materials and preparation thereof, and particularly relates to a biological melanin/graphene composite material and a preparation method and application thereof.
Background
The microbial fuel cell directly converts chemical energy into electric energy, and has the characteristics of high energy conversion efficiency, strong electricity generation power density, greenness, cleanness, no pollution and the like compared with the traditional cell, thereby being widely concerned. The power generation efficiency of a microbial fuel cell depends on various factors, wherein the electron transfer efficiency of the cathode material directly affects the overall performance of the microbial fuel cell. Therefore, in order to further enhance the electron transfer efficiency, researchers are continuously searching for cathode materials. In recent years, graphene has attracted much attention because of its advantages such as large specific surface area, good electrical conductivity, and high mechanical strength. In order to further improve the electrochemical performance of graphene, researchers mix non-metallic heteroatoms (such as N, S, P, etc.) in graphene to tune its conductivity, and on the other hand, researchers compound graphene with other substances to prepare composite materials (such as Co)3O4A/graphene composite material and a Pt/Pb/graphene composite material) to improve the electrochemical performance of graphene. However, the current composite materials or doped materials suffer from the defects of complex preparation process, high cost and the like, and limit the mass production and wide application of the composite materials or doped materials in practice. It is also noted that the biocompatibility of the composite material is a key factor in determining whether it can be applied to microbial fuel cells. Therefore, finding a more suitable substance to combine with graphene to form a complex is the key to improve the productivity and performance.
In recent years, some biological pigments have been found to catalyze the removal of various refractory organic pollutants as a mediator of redox reactions. Among them, melanin is an important biological pigment, whose chemical composition and molecular structure are very similar to those of humus, and can be used as an electron medium to accelerate electron transfer of natural biological geochemical conversion. However, melanin runs off along with the effluent, causing secondary pollution to the environment, and meanwhile, in order to ensure the electrochemical efficacy, the continuous addition of melanin also causes the problem of increasing the operation cost. In addition, melanin is currently obtained by extraction from animals and plants, or by means of artificial chemical synthesis. The chemical synthesis reaction is complex and has certain toxicity, which limits the further application of melanin.
In view of the conductivity of the graphene raw material and the electron transfer characteristic of the biological melanin, if the two materials can be compounded together to form a nonmetal composite material, the electrochemical performance of the graphene is improved, the biological melanin can be fixed, the biocompatibility of the composite material can be further solved, and the electricity production efficiency of the microbial fuel cell is finally improved.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to provide a biological melanin/graphene composite material, and a preparation method and application thereof. The biological melanin/graphene nanocomposite is coated on one side of a load platform and dried to obtain a biological melanin/graphene modified electrode, and the biological melanin/graphene modified electrode is used as a cathode of a microbial fuel cell and applied to the microbial fuel cell, has high electricity generation efficiency and can stably run for a long time.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a method for preparing a biological melanin/graphene composite material, comprising the steps of:
1) mixing biological melanin with N, N-dimethylacetamide and heating to obtain a biological melanin solution;
2) mixing and heating the biological melanin solution obtained in the step 1), the carboxylated graphene and the acidic solution to obtain a first mixture;
3) carrying out microwave catalytic reaction on the first mixture obtained in the step 2) to obtain a second mixture;
4) carrying out ultrasonic treatment on the second mixture obtained in the step 3) to obtain a third mixture;
5) centrifuging, washing and drying the third mixture obtained in the step 4) to obtain the biological melanin/graphene nano composite material.
Preferably, step 1) further comprises at least one of the following technical features:
1) the volume ratio of the mass of the biological melanin to the volume of the N, N-dimethylacetamide is 200mg:100 mL-400 mg:100mL, such as 200mg:100 mL-300 mg:100mL or 300mg:100 mL-400 mg:100 mL;
2) the heating temperature is 55-65 deg.C, such as 55-60 deg.C or 60-65 deg.C.
Preferably, step 2) further comprises at least one of the following technical features:
1) the mass ratio of the biological melanin to the carboxylated graphene is 1: 1-2: 1, such as 1: 1-1.5: 1 or 1.5: 1-2: 1;
2) the acidic solution is selected from at least one of hydrochloric acid and sulfuric acid;
3) the volume ratio of the acidic solution to the N, N-dimethylacetamide is 0.3: 100-0.5: 100, such as 0.3: 100-0.4: 100 or 0.4: 100-0.5: 100;
4) the heating temperature is 75-85 deg.C, such as 75-80 deg.C or 80-85 deg.C;
5) the heating time is 1.8 h-2.2 h, such as 1.8 h-2 h or 2 h-2.2 h.
More preferably, in the feature 2), the concentration of the hydrochloric acid is 36 to 38 wt%, and the concentration of the concentrated sulfuric acid is 97 to 99 wt%.
Preferably, at least one of the following technical features is also included:
1) in the step 3), the microwave catalytic reaction temperature is 90-120 ℃, such as 90-110 ℃ or 110-120 ℃;
2) in the step 3), the microwave catalytic reaction time is 18min to 22min, such as 18min to 20min or 20min to 22 min;
3) in the step 3), the microwave catalytic reaction power is 500W-700W, such as 500W-600W or 600W-700W;
4) in the step 4), the ultrasonic treatment time is 1.35 h-1.65 h, such as 1.35 h-1.5 h or 1.5 h-1.65 h;
5) in the step 4), the ultrasonic frequency is 30 kHz-50 kHz, such as 30 kHz-40 kHz or 40 kHz-50 kHz.
Preferably, step 5) further comprises at least one of the following technical features:
1) washing with N, N-dimethylacetamide and/or water;
2) the drying temperature is 55-65 deg.C, such as 55-60 deg.C or 60-65 deg.C;
3) the drying time is 46 h-50 h, such as 46 h-48 h or 48 h-50 h;
4) drying under vacuum condition, wherein the relative vacuum degree is 0.05 MPa-0.07 MPa, such as 0.05 MPa-0.06 MPa or 0.06 MPa-0.07 MPa.
The second aspect of the invention provides a biological melanin/graphene composite material obtained by the preparation method.
The third aspect of the invention provides an application of the biological melanin/graphene composite material in power generation of a microbial fuel cell.
Preferably, the biological melanin/graphene composite material is coated on one side of a loading platform and dried to obtain a biological melanin/graphene modified electrode as a cathode of a microbial fuel cell.
More preferably, at least one of the following technical characteristics is also included:
1) the load platform is carbon cloth;
2) the load capacity of the biological melanin/graphene composite material is 0.05mg/cm2～0.15mg/cm2E.g. 0.05mg/cm2～0.1mg/cm2Or 0.1mg/cm2～0.15mg/cm2。
The technical scheme has the following beneficial effects:
(1) the biological melanin/graphene nano composite material is coated on one side of a load platform and dried to obtain a biological melanin/graphene modified electrode, and the biological melanin/graphene modified electrode is used as a cathode of a microbial fuel cell and applied to the microbial fuel cell, has high electricity generation efficiency and can stably run for a long time.
(2) The biological melanin/graphene nano composite material can be applied to microbial fuel cells in an industrialized and large-scale manner, and the electricity generation efficiency and the biocompatibility of the microbial fuel cells are further improved.
(3) The preparation method solves the problem of immobilization of biological melanin, and has the advantages of simple process, short period and environmental friendliness.
Detailed Description
The technical solution of the present invention is illustrated by specific examples below. It is to be understood that one or more method steps mentioned in the present invention do not exclude the presence of other method steps before or after the combination step or that other method steps may be inserted between the explicitly mentioned steps; it should also be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1
The preparation method of the biological melanin/graphene composite material in the embodiment comprises the following steps:
(1) adding 300mg of biological melanin into 100mL of N, N-dimethylacetamide, and heating to 60 ℃ to obtain a dark brown solution;
(2) adding 150mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of the biological melanin to the carboxylated graphene is 2:1, and adding 0.4mL of concentrated hydrochloric acid (the concentration is 36 wt%), and heating in a water bath at 80 ℃ for 2 hours to obtain a first mixture;
(3) putting the first mixture obtained in the step (2) into a microwave reactor for microwave catalytic reaction, wherein the reaction temperature of the microwave catalytic reaction is 120 ℃, the reaction time is 20min, and the reaction power is 700W, so as to obtain a second mixture;
(4) carrying out ultrasonic treatment on the second mixture obtained in the step (3) for 1.5h at 40 kHz;
(5) centrifuging the second mixture subjected to ultrasonic treatment in the step (4) by a high-speed centrifuge at 12000rpm for 10min, then repeatedly washing the mixture by deionized water, and performing vacuum drying at the relative vacuum degree of 0.06MPa and the temperature of 60 ℃ for 48h to obtain the biological melanin/graphene composite material;
the biological melanin/graphene composite material is applied to electricity generation of a microbial fuel cell:
(6) uniformly coating the composite material obtained in the step (5) on one side of the carbon cloth, wherein the effective content is 0.1mg/cm2Naturally air-drying for 24 hours at room temperature to obtain a biological melanin/graphene modified electrode;
(7) and (4) taking the biological melanin/graphene modified electrode obtained in the step (6) as a cathode of the microbial fuel cell, connecting to an external circuit of the 1000 omega air cathode single-chamber microbial fuel cell, and performing a performance test on the fuel cell after the highest voltage output is stable.
The maximum output voltage of the microbial fuel cell with the graphene catalytic electrode as the cathode is 0.195V, and the maximum output power is 117mW/m2The highest output voltage obtained by the microbial fuel cell with the biological melanin/graphene modified electrode as the cathode is increased from 0.195V to 0.254V, which is increased by 30.2%; the maximum output power is 117mW/m2The output is increased to 192mW/m2The improvement is 64.1%.
Example 2
This example differs from example 1 in that: and (3) adding 200mg of carboxylated graphene in the step (2), wherein the mass ratio of the biological melanin to the carboxylated graphene is 1.5: 1. The other steps and parameters were the same as in example 1. Under the conditions described in this example, the maximum output voltage of the microbial fuel cell using the biological melanin/graphene modified electrode as the cathode is increased from 0.195V to 0.233V, which is increased by 19.5%; the maximum output power is 117mW/m2The total weight is increased to 178mW/m2The improvement is 52.1%.
Example 3
The preparation method of the biological melanin/graphene composite material in the embodiment comprises the following steps:
(1) adding 200mg of biological melanin into 100mL of N, N-dimethylacetamide, and heating to 55 ℃ to obtain a dark brown solution;
(2) adding 200mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of the biological melanin to the carboxylated graphene is 1:1, and adding 0.5mL of concentrated hydrochloric acid (the concentration is 38 wt%), and heating in a water bath at 75 ℃ for 2.2 hours to obtain a first mixture;
(3) putting the first mixture obtained in the step (2) into a microwave reactor for microwave catalytic reaction, wherein the reaction temperature of the microwave catalytic reaction is 90 ℃, the reaction time is 22min, and the reaction power is 600W, so as to obtain a second mixture;
(4) carrying out ultrasonic treatment on the second mixture obtained in the step (3) for 1.35h at 50 kHz;
(5) centrifuging the second mixture subjected to ultrasonic treatment in the step (4) for 10min at 12000rpm by a high-speed centrifuge, repeatedly washing the mixture by using N, N-dimethylacetamide, and performing vacuum drying for 50h at the relative vacuum degree of 0.07MPa and the temperature of 55 ℃ to obtain the biological melanin/graphene composite material;
the biological melanin/graphene composite material is applied to electricity generation of a microbial fuel cell:
(6) uniformly coating the composite material obtained in the step (5) on one side of the carbon cloth, wherein the effective content is 0.05mg/cm2Naturally air-drying for 24 hours at room temperature to obtain a biological melanin/graphene modified electrode;
(7) and (4) taking the biological melanin/graphene modified electrode obtained in the step (6) as a cathode of the microbial fuel cell, connecting to an external circuit of the 1000 omega air cathode single-chamber microbial fuel cell, and performing a performance test on the fuel cell after the highest voltage output is stable.
The maximum output voltage of the microbial fuel cell with the graphene catalytic electrode as the cathode is 0.195V, and the maximum output power is 117mW/m2The highest output voltage obtained by the microbial fuel cell with the biological melanin/graphene modified electrode as the cathode is increased from 0.195V to 0.213V, which is increased by 9.2%; the maximum output power is 117mW/m2The total weight is increased to 166mW/m2The improvement is 41.9%.
Example 4
The preparation method of the biological melanin/graphene composite material in the embodiment comprises the following steps:
(1) adding 400mg of biological melanin into 100mL of N, N-dimethylacetamide, and heating to 65 ℃ to obtain a dark brown solution;
(2) adding 200mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of the biological melanin to the carboxylated graphene is 2:1, and adding 0.3mL of concentrated sulfuric acid (the concentration is 97 wt%), and heating in a water bath at 85 ℃ for 1.8h to obtain a first mixture;
(3) putting the first mixture obtained in the step (2) into a microwave reactor for microwave catalytic reaction, wherein the reaction temperature of the microwave catalytic reaction is 110 ℃, the reaction time is 18min, and the reaction power is 500W, so as to obtain a second mixture;
(4) carrying out ultrasonic treatment on the second mixture obtained in the step (3) for 1.65h at 30 kHz;
(5) centrifuging the second mixture subjected to ultrasonic treatment in the step (4) for 10min at 12000rpm by a high-speed centrifuge, repeatedly washing the mixture by using N, N-dimethylacetamide, and drying the mixture for 46h under the conditions that the relative vacuum degree is 0.05MPa and the temperature is 65 ℃ in vacuum to obtain the biological melanin/graphene composite material;
the biological melanin/graphene composite material is applied to electricity generation of a microbial fuel cell:
(6) uniformly coating the composite material obtained in the step (5) on one side of the carbon cloth, wherein the effective content is 0.15mg/cm2Naturally air-drying for 24 hours at room temperature to obtain a biological melanin/graphene modified electrode;
(7) and (4) taking the biological melanin/graphene modified electrode obtained in the step (6) as a cathode of the microbial fuel cell, connecting to an external circuit of the 1000 omega air cathode single-chamber microbial fuel cell, and performing a performance test on the fuel cell after the highest voltage output is stable.
The maximum output voltage of the microbial fuel cell with the graphene catalytic electrode as the cathode is 0.195V, and the maximum output power is 117mW/m2The highest output voltage obtained by the microbial fuel cell with the biological melanin/graphene modified electrode as the cathode is increased from 0.195V to 0.236V, which is increased by 21.0%; the maximum output power is 117mW/m2The yield is increased to 181mW/m2Improve and increase54.7％。
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a biological melanin/graphene composite material is characterized by comprising the following steps:
1) mixing biological melanin with N, N-dimethylacetamide and heating to obtain a biological melanin solution;
2) mixing and heating the biological melanin solution obtained in the step 1), the carboxylated graphene and the acidic solution to obtain a first mixture;
3) carrying out microwave catalytic reaction on the first mixture obtained in the step 2) to obtain a second mixture;
4) carrying out ultrasonic treatment on the second mixture obtained in the step 3) to obtain a third mixture;
5) centrifuging, washing and drying the third mixture obtained in the step 4) to obtain the biological melanin/graphene nano composite material.
2. The method for preparing the biological melanin/graphene composite material according to claim 1, wherein the step 1) further comprises at least one of the following technical features:
1) the volume ratio of the mass of the biological melanin to the N, N-dimethylacetamide is 200mg:100 mL-400 mg:100 mL;
2) the heating temperature is 55-65 ℃.
3. The method for preparing the biological melanin/graphene composite material according to claim 1, wherein the step 2) further comprises at least one of the following technical features:
1) the mass ratio of the biological melanin to the carboxylated graphene is 1: 1-2: 1;
2) the acidic solution is selected from at least one of hydrochloric acid and sulfuric acid;
3) the volume ratio of the acidic solution to the N, N-dimethylacetamide is 0.3: 100-0.5: 100;
4) the heating temperature is 75-85 ℃;
5) the heating time is 1.8 h-2.2 h.
4. The method according to claim 3, wherein the concentration of hydrochloric acid is 36-38 wt% and the concentration of concentrated sulfuric acid is 97-99 wt% in the step 2).
5. The method for preparing biological melanin/graphene composite material according to claim 1, further comprising at least one of the following technical features:
1) in the step 3), the microwave catalytic reaction temperature is 90-120 ℃;
2) in the step 3), the microwave catalytic reaction time is 18-22 min;
3) in the step 3), the microwave catalytic reaction power is 500W-700W;
4) in the step 4), the ultrasonic treatment time is 1.35-1.65 h;
5) in the step 4), the ultrasonic frequency is 30 kHz-50 kHz.
6. The method for preparing the biological melanin/graphene composite material according to claim 1, wherein the step 5) further comprises at least one of the following technical characteristics:
1) washing with N, N-dimethylacetamide and/or water;
2) the drying temperature is 55-65 ℃;
3) the drying time is 46-50 h;
4) drying under vacuum condition, wherein the relative vacuum degree is 0.05 MPa-0.07 MPa.
7. A biological melanin/graphene composite material obtained by the preparation method of any one of claims 1 to 6.
8. The use of the biological melanin/graphene composite material of claim 7 in the production of electricity by a microbial fuel cell.
9. The use of the biological melanin/graphene composite material according to claim 8, wherein the biological melanin/graphene composite material is coated on one side of a loading platform and dried to obtain a biological melanin/graphene modified electrode as a cathode of a microbial fuel cell.
10. The use of biological melanin/graphene composite material according to claim 9, further comprising at least one of the following technical features:
1) the load platform is carbon cloth;
2) the load capacity of the biological melanin/graphene composite material is 0.05mg/cm2～0.15mg/cm2。
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| CN103592350A (en) * | 2013-11-25 | 2014-02-19 | 信阳师范学院 | Melanin nanoparticle-graphene electrochemical sensor as well as preparation method and application thereof |
| CN107331870A (en) * | 2017-06-09 | 2017-11-07 | 同济大学 | A kind of preparation method of graphene/riboflavin composite |
| CN111733472A (en) * | 2020-06-01 | 2020-10-02 | 上海烯望材料科技有限公司 | Composite material composed of graphene oxide and melanin, and preparation method and application thereof |
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