CN112349917A - Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof - Google Patents

Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof Download PDF

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CN112349917A
CN112349917A CN202011144144.6A CN202011144144A CN112349917A CN 112349917 A CN112349917 A CN 112349917A CN 202011144144 A CN202011144144 A CN 202011144144A CN 112349917 A CN112349917 A CN 112349917A
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melanin
graphene
mixture
graphene nanocomposite
nanocomposite material
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CN112349917B (en
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郑雄
吴瑒
陈银广
黄海宁
胡婉莹
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Tongji University
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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
    • 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
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a melanin/graphene nano composite material for improving electron transfer efficiency and a preparation method and application thereof. The preparation method comprises the following steps: 1) mixing melanin and N, N-dimethylacetamide and heating to obtain a melanin solution; 2) mixing and heating a melanin solution, carboxylated graphene and an acidic solution to obtain a first mixture; 3) calcining the first mixture to obtain a second mixture; 4) carrying out ultrasonic treatment on the second mixture to obtain a third mixture; 5) and washing and drying the third mixture to obtain the melanin/graphene nanocomposite. The preparation method has the advantages of simple process, low cost, short period and environmental friendliness, is suitable for industrial large-scale production, and the prepared composite material has good conductivity, high electron transfer efficiency and wide application range, and can be applied to the aspects of fuel cell power generation, removal of refractory organic matters, reduction of heavy metals and the like.

Description

Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials and preparation thereof, and particularly relates to a melanin/graphene nano composite material for improving electron transfer efficiency, and a preparation method and application thereof.
Background
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.
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, which is a redox mediator secreted by microorganisms itself, has excellent electron transfer properties and unique amorphous semiconductor properties, and has attracted extensive attention of researchers. However, melanin runs off along with effluent, secondary pollution is caused to the environment, and continuous addition of melanin for ensuring electrochemical efficacy also causes the problem of increased operation cost, and further application of melanin is limited.
In view of the conductivity of the graphene raw material and the electron transfer characteristic of the melanin, if the two materials can be compounded together to form a nonmetal composite material, the electrochemical performance of the graphene is improved, and the melanin can be fixed. The composite material is expected to have more excellent performance than the two materials independently, and the application field of the composite material can be further widened.
Disclosure of Invention
In view of the above-mentioned disadvantages of the prior art, the present invention aims to provide a melanin/graphene nanocomposite material with improved electron transfer efficiency, and a preparation method and application thereof. The preparation method has the advantages of simple process, low cost, short period and environmental friendliness, is suitable for industrial large-scale production, and the prepared composite material has good conductivity, high electron transfer efficiency and wide application range, and can be applied to the aspects of fuel cell power generation, removal of refractory organic matters, reduction of heavy metals and the like.
In order to achieve the above objects and other related objects, a first aspect of the present invention provides a method for preparing a melanin/graphene nanocomposite, comprising the steps of:
1) mixing melanin and N, N-dimethylacetamide and heating to obtain a melanin solution;
2) mixing and heating the melanin solution, the carboxylated graphene and the acidic solution obtained in the step 1) to obtain a first mixture;
3) calcining 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) washing and drying the third mixture obtained in the step 4) to obtain the melanin/graphene nano composite material.
Preferably, step 1) further comprises at least one of the following technical features:
1) n, N-dimethylacetamide is used to dissolve melanin, and the amount thereof can be controlled as desired, for example: the volume ratio of the mass of the melanin to the volume of the N, N-dimethylacetamide can be 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 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, in step 3), the calcination temperature is 200 ℃ to 400 ℃, such as 200 ℃ to 300 ℃, 300 ℃ to 350 ℃ or 350 ℃ to 400 ℃.
Preferably, in step 3), the calcination time is 1h to 3h, such as 1h to 2h or 2h to 3 h.
Preferably, step 4) further comprises at least one of the following technical features:
1) 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;
2) 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 melanin/graphene nanocomposite material obtained by the preparation method.
The third aspect of the invention provides the application of the melanin/graphene nanocomposite material in power generation of fuel cells, organic matter removal and heavy metal reduction.
The technical scheme has the following beneficial effects:
(1) the melanin/graphene nano composite material prepared by the preparation method improves the electrochemical performance of graphene and solves the problem of melanin immobilization, has good conductivity, high electron transfer efficiency and wide application range, and can be applied to the aspects of fuel cell power generation, removal of refractory organic matters, reduction of heavy metals and the like.
(2) The preparation method solves the problem of melanin immobilization, has the advantages of simple process, low cost, short period and environmental friendliness, and is suitable for industrial large-scale production of melanin/graphene nano composite materials.
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 melanin/graphene nanocomposite material in the embodiment comprises the following steps:
(1) adding 300mg of melanin into 100mL of N, N-dimethylacetamide, and heating to 60 ℃ to obtain a dark brown solution, namely a melanin solution;
(2) adding 150mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of melanin to the carboxylated graphene is 2:1, adding 0.4mL of concentrated hydrochloric acid (the purity is 36%), 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 tubular muffle furnace for calcination synthesis, wherein the reaction temperature of the calcination synthesis is 300 ℃, and the reaction time is 2 hours, 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 40kHz to obtain a third mixture;
(5) repeatedly washing the third mixture obtained in the step (4) with N, N-dimethylacetamide and deionized water, and drying in vacuum at a relative vacuum degree of 0.06MPa and a temperature of 60 ℃ for 48 hours to obtain the melanin/graphene nanocomposite material with a diameter of 1-5 um and a thickness of 0.8-1.2 nm.
The prepared melanin/graphene nanocomposite material is subjected to electrochemical performance promotion test by an electrochemical workstation according to the following steps: respectively taking the melanin/graphene nanocomposite material and the graphene raw material prepared in the embodiment as working electrodes of an electrochemical workstation; performing cyclic voltammetry test in oxygen-saturated PBS solution at a scanning speed of 0.05V/s and a scanning range of-1.0 to + 1.0V; and carrying out alternating current impedance test under the condition that the frequency scanning range is 0.1-10000 Hz. The maximum current density obtained by taking a graphene raw material as a working electrode is 0.24mA/cm2The charge transfer impedance is 5342 omega, and the maximum current density obtained by using the melanin/graphene nano composite material as the working electrode is 0.24mA/cm2Lifting to 1.09mA/cm2The improvement is 354%; the charge transfer impedance is reduced from 5342 Ω to 253 Ω, a 95% reduction.
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 melanin to the carboxylated graphene is 1.5: 1. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 0.98mA/cm2The yield is improved by 200%; the charge transfer impedance is reduced from 5342 Ω to 355 Ω, which is 84% lower.
Example 3
This example differs from example 1 in that: and (3) adding 300mg of carboxylated graphene in the step (2), wherein the mass ratio of the melanin to the carboxylated graphene is 1: 1. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 0.63mA/cm2The improvement is 163%; the charge transfer impedance is reduced from 5342 Ω to 1003 Ω, which is 81%.
Example 4
This example differs from example 1 in that: in step (2), 0.4mL of concentrated sulfuric acid (98% purity) was added. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 0.98mA/cm2The yield is improved by 308%; the charge transfer impedance is reduced from 5342 Ω to 1003 Ω, which is 93%.
Example 5
This example differs from example 1 in that: the reaction temperature for calcination synthesis in the step (3) is 200 ℃. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 0.52mA/cm2The yield is improved by 117%; the charge transfer impedance is reduced from 5342 Ω to 1923 Ω, a 64% reduction.
Example 6
This example differs from example 1 in that: the reaction temperature for calcination synthesis in the step (3) is 400 ℃. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 0.74mA/cm2The yield is improved by 117%; the charge transfer impedance is reduced from 5342 Ω to 679 Ω, which is 87%.
Example 7
This example differs from example 1 in that: and (4) performing ultrasonic treatment for 1.5h at 30 kHz. The other steps and parameters were the same as in example 1. This implementationExample the maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described was from 0.24mA/cm2Lifting to 0.95mA/cm2The yield is improved by 296 percent; the charge transfer impedance is reduced from 5342 Ω to 377 Ω, which is 93%.
Example 8
This example differs from example 1 in that: and (4) performing ultrasonic treatment for 1.5h at 50 kHz. The other steps and parameters were the same as in example 1. The maximum current density obtained with the melanin/graphene nanocomposite as the working electrode under the conditions described in this example was from 0.24mA/cm2Lifting to 1.03mA/cm2The yield is improved by 329 percent; the charge transfer resistance decreases from 5342 Ω to 287 Ω, a 94% decrease.
Example 9
The preparation method of the melanin/graphene nanocomposite material in the embodiment comprises the following steps:
(1) adding 200mg of melanin into 100mL of N, N-dimethylacetamide, and heating to 65 ℃ to obtain a dark brown solution, namely a melanin solution;
(2) adding 150mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of melanin to the carboxylated graphene is 1.33:1, adding 0.5mL of concentrated hydrochloric acid (the purity is 38%), and heating in a water bath at 85 ℃ for 1.8 hours to obtain a first mixture;
(3) putting the first mixture obtained in the step (2) into a tubular muffle furnace for calcination synthesis, wherein the reaction temperature of the calcination synthesis is 350 ℃, and the reaction time is 3 hours, 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 40kHz to obtain a third mixture;
(5) and (4) repeatedly washing the third mixture obtained in the step (4) with N, N-dimethylacetamide and deionized water, and drying for 50 hours in vacuum at the relative vacuum degree of 0.07MPa and the temperature of 65 ℃ to obtain the melanin/graphene nanocomposite.
The prepared melanin/graphene nanocomposite material is subjected to electrochemical performance promotion test by an electrochemical workstation according to the following steps: are respectively provided withTaking the melanin/graphene nanocomposite material and the graphene raw material prepared in the embodiment as working electrodes of an electrochemical workstation; performing cyclic voltammetry test in oxygen-saturated PBS solution at a scanning speed of 0.05V/s and a scanning range of-1.0 to + 1.0V; and carrying out alternating current impedance test under the condition that the frequency scanning range is 0.1-10000 Hz. The maximum current density obtained by taking a graphene raw material as a working electrode is 0.24mA/cm2The charge transfer impedance is 5342 omega, and the maximum current density obtained by using the melanin/graphene nano composite material as the working electrode is 0.24mA/cm2Lifting to 0.82mA/cm2The yield is increased by 242%; the charge transfer impedance is reduced from 5342 Ω to 651 Ω by 88%.
Example 10
The preparation method of the melanin/graphene nanocomposite material in the embodiment comprises the following steps:
(1) adding 400mg of melanin into 100mL of N, N-dimethylacetamide, and heating to 55 ℃ to obtain a dark brown solution, namely a melanin solution;
(2) adding 200mg of carboxylated graphene into the dark brown solution obtained in the step (1), wherein the mass ratio of melanin to the carboxylated graphene is 2:1, adding 0.3mL of concentrated sulfuric acid (with the purity of 99%), 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 tubular muffle furnace for calcination synthesis, wherein the reaction temperature of the calcination synthesis is 350 ℃, and the reaction time is 1h, 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 50kHz to obtain a third mixture;
(5) repeatedly washing the third mixture obtained in the step (4) with N, N-dimethylacetamide and deionized water, and drying for 46h under the conditions that the relative vacuum degree is 0.05MPa and the temperature is 55 ℃ in vacuum to obtain the melanin/graphene nanocomposite.
The prepared melanin/graphene nanocomposite material is subjected to electrochemical performance promotion test by an electrochemical workstation according to the following steps: respectively in the above-mentioned embodimentsThe prepared melanin/graphene nanocomposite and graphene raw materials are used as working electrodes of an electrochemical workstation; performing cyclic voltammetry test in oxygen-saturated PBS solution at a scanning speed of 0.05V/s and a scanning range of-1.0 to + 1.0V; and carrying out alternating current impedance test under the condition that the frequency scanning range is 0.1-10000 Hz. The maximum current density obtained by taking a graphene raw material as a working electrode is 0.24mA/cm2The charge transfer impedance is 5342 omega, and the maximum current density obtained by using the melanin/graphene nano composite material as the working electrode is 0.24mA/cm2Lifting to 0.92mA/cm2The yield is improved by 283%; the charge transfer impedance is reduced from 5342 Ω to 461 Ω, which is a 91% reduction.
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 melanin/graphene nano composite material is characterized by comprising the following steps:
1) mixing melanin and N, N-dimethylacetamide and heating to obtain a melanin solution;
2) mixing and heating the melanin solution, the carboxylated graphene and the acidic solution obtained in the step 1) to obtain a first mixture;
3) calcining 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) washing and drying the third mixture obtained in the step 4) to obtain the melanin/graphene nano composite material.
2. The method for preparing the melanin/graphene nanocomposite material according to claim 1, wherein the step 1) further comprises at least one of the following technical characteristics:
1) the volume ratio of the mass of the melanin to the volume of 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 melanin/graphene nanocomposite 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 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 hydrochloric acid has a concentration of 36 to 38 wt% and the concentrated sulfuric acid has a concentration of 97 to 99 wt% in the step 2).
5. The method for preparing the melanin/graphene nanocomposite material according to claim 1, wherein the calcination temperature in the step 3) is 200 to 400 ℃.
6. The method for preparing the melanin/graphene nanocomposite material according to claim 1, wherein in the step 3), the calcination time is 1 to 3 hours.
7. The method for preparing the melanin/graphene nanocomposite material according to claim 1, wherein the step 4) further comprises at least one of the following technical characteristics:
1) the ultrasonic treatment time is 1.35 h-1.65 h;
2) the ultrasonic frequency is 30 kHz-50 kHz.
8. The method for preparing the melanin/graphene nanocomposite 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.
9. A melanin/graphene nanocomposite obtained by the production method according to any one of claims 1 to 8.
10. Use of the melanin/graphene nanocomposite of claim 9 in fuel cell power generation, organic matter removal, and heavy metal reduction.
CN202011144144.6A 2020-10-23 2020-10-23 Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof Active CN112349917B (en)

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