CN107331870A - A kind of preparation method of graphene/riboflavin composite - Google Patents
A kind of preparation method of graphene/riboflavin composite Download PDFInfo
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- CN107331870A CN107331870A CN201710429671.3A CN201710429671A CN107331870A CN 107331870 A CN107331870 A CN 107331870A CN 201710429671 A CN201710429671 A CN 201710429671A CN 107331870 A CN107331870 A CN 107331870A
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- riboflavin
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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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
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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
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Abstract
The present invention proposes a kind of preparation method of graphene/riboflavin composite, comprises the following steps：Riboflavin is added in N, N dimethyl acetamides, heated；Add carboxylated graphene and concentrated hydrochloric acid, heating water bath；Mixture is put into microwave reactor, microwave catalysis reaction is carried out；Reacted mixture is cooled down；Mixture is carried out ultrasonically treated；With N, N dimethyl acetamides and deionized water are rinsed repeatedly, wash away unreacted reactant；Reaction product is dried in vacuo.The electron transmission efficiency of graphene prepared by the present invention/riboflavin composite is high, has a wide range of application, and can be applicable in terms of fuel cell electricity production, water pollutant degraded.The inventive method has that technique is simple, with low cost, the cycle is short, environment-friendly, is applicable to industrialization large-scale production graphene/riboflavin composite.
Description
Technical field
The invention belongs to new energy materialses and its preparing technical field, it is related to a kind of graphene/riboflavin composite
Preparation method.
Background technology
Chemical energy can be converted into electric energy by fuel cell, while having high conversion efficiency, power density height, noise
Small, pollution-free the advantages of, therefore receive significant attention.In the factors of influence energy conversion, the oxygen reduction on negative electrode
Leading factor is reacted to, electron transmission efficiency therein directly affects the overall performance of battery.In order to promote oxygen reduction
Course of reaction and electron transport rate, additional catalyst turn into the means that researcher pays close attention to.In recent years, graphene because its
Energy change and electron transmission in unique effect and obtain extensive concern, in order to further improve graphene electric conductivity and
Durability, researchers are made that many effort.Many researchers pass through nonmetallic heteroatoms of being adulterated in graphene（Such as N, S,
P etc.）To tune its electric conductivity, also there is researcher by the way that graphene and other materials are combined, prepare composite
（Such as Co3O4/ graphene composite material and Co3O4/ graphene composite material）To improve the chemical property of graphene.However, mesh
Preceding composite or dopant material is faced with the defect that cost of manufacture is high and preparation technology is complicated, and which has limited the extensive of it
Production and application.It is further noted that the biocompatibility of composite is to determine whether it can apply to microorganism
The key factor of fuel cell.Therefore, it is to improve electron transmission to find more suitably material and graphene and combine to form compound
Key.
Recent study finds that some organic molecules are as the amboceptor of redox reaction to various organic and inorganic pollution
The redox of thing removes and plays catalytic action.Wherein, riboflavin（Also known as vitamin B2）As redox mediator, cause
The extensive concern of researcher, is progressively produced electricity in the removal process with pollutant applied to fuel cell.But, riboflavin it is solvable
Property prevents it from retaining in the reactor, it is necessary to be continuously added into, and which greatly enhances the cost of reaction, limits entering for riboflavin
One step application.
In view of the electric conductivity and the solubility of riboflavin of graphene raw material, if can be by two kinds of Material claddings one
Rise, form a kind of nonmetallic composite, this is the chemical property and biocompatibility for improving graphene, while can be real
Now to the fixation of riboflavin.The composite expection can further widen it by with than both independent more excellent performances
Application field.
The content of the invention
It is contemplated that at least solving one of technical problem in correlation technique to a certain extent.
Therefore, it is an object of the present invention to the chemical property and biocompatibility for raising graphene and solving core
The immobilization problem of flavine and the preparation method that a kind of graphene/riboflavin composite is provided.
A kind of preparation method of graphene/riboflavin composite according to embodiments of the present invention, comprises the following steps：
（1）Riboflavin is added in DMA, yellow solution is obtained after heating；
（2）To step（1）First is obtained in obtained yellow solution after addition carboxylated graphene and concentrated hydrochloric acid, heating water bath to mix
Compound；The mass ratio of riboflavin and carboxylated graphene is 1:1~2:1, the concentration of concentrated hydrochloric acid is 12mol/L, concentrated hydrochloric acid and N,
The volume ratio of N- dimethyl acetamides is 0.4:100；
（3）By step（2）The first obtained mixture is put into microwave reactor, carries out microwave catalysis reaction, is obtained second and is mixed
Compound；The reaction temperature of microwave catalysis reaction is 80 DEG C~150 DEG C, and the reaction time is 20min ± 2min, and reaction power is 500W
~900W；
（4）By step（3）The second obtained mixture carries out ultrasonically treated；
（5）By step（4）Repeatedly, vacuum is done for the second mixture DMA and deionized water rinsing after processing
Graphene/riboflavin composite is obtained after dry.
In the present invention, the step（1）In, heating-up temperature is 60 DEG C ± 5 DEG C.
In the present invention, the step（2）In, the temperature of heating water bath is 80 DEG C ± 5 DEG C, and the time is 2 h ± 0.2h.
In the present invention, the step（3）In, the reaction temperature of microwave catalysis reaction is 120 DEG C, and the reaction time is 20min,
Reaction power is 700W.
In the present invention, the step（4）In, the ultrasonically treated time is 1.5h ± 0.15h, and ultrasound condition is low frequency.
In the present invention, the step（5）In, vacuum drying temperature is 60 DEG C ± 5 DEG C, and the time is 48h ± 2h, relatively very
Reciprocal of duty cycle is 0.05MPa~0.07MPa.
The invention has the advantages that：
Graphene prepared by the present invention/riboflavin composite electrochemical performance, has a wide range of application, and can be used in fuel electricity
The fields such as pond, the redox removal of pollutant.The inventive method has that technique is simple, with low cost, the cycle is short, environment-friendly
The advantages of, it can try out and mass produce graphene/riboflavin composite in industrialization.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
The present invention is further described with reference to specific embodiment.
Embodiment 1
The preparation method of graphene/riboflavin composite is completed by following step in the present embodiment：
（1）300mg riboflavin is added in 100mL DMA, 60 DEG C is heated to, obtains yellow solution；
（2）To step（1）150mg carboxylated graphenes, riboflavin and carboxylated graphene are added in obtained yellow solution
Mass ratio is 2:1, add 0.4 mL concentrated hydrochloric acids（Concentration is 12mol/L）, 80 DEG C of h of heating water bath 2 obtain the first mixture；
（3）By step（2）The first obtained mixture is put into microwave reactor, carries out microwave catalysis reaction, and microwave catalysis is anti-
The reaction temperature answered is 120 DEG C, and the reaction time is 20min, and reaction power is 700W, obtains the second mixture；
（4）By step（3）The second obtained mixture carries out ultrasonically treated, ultrasonically treated 1.5h under low frequency condition
（5）By step（4）The second mixture after ultrasonically treated is rinsed repeatedly with DMA and deionized water,
Relative degree of vacuum is that 0.05MPa~0.07MPa, temperature are to be dried in vacuo after 48 h at 60 DEG C, you can obtain graphene/riboflavin
Composite.
The promotion electron transmission performance test of prepared graphene/riboflavin composite utilizes single-chamber microbial fuel
Battery is carried out in the steps below：15mL electricity-producing microorganism bacterium solution is added at air cathode single chamber MFC imports, more than difference
Graphene/riboflavin composite the catalysis electrode and graphene catalysis electrode for stating embodiment preparation are used as the moon of fuel cell
Pole；By 1000 ohm of air cathode single chamber MFC external circuit of fuel cell access, start recording electricity generation process treats ceiling voltage
The performance test of fuel cell is carried out after output is stable.The highest that MFC using graphene catalysis electrode as negative electrode is obtained is defeated
It is respectively 0.42V and 650mW/m to go out voltage and peak power output2, using graphene/riboflavin composite catalysis electrode as
The maximum output voltage and peak power output that the MFC of negative electrode is obtained are respectively 0.46V and 810mW/m2。
Embodiment 2
The present embodiment is as different from Example 1：Step（2）Add 200 mg carboxylated graphenes, riboflavin and carboxyl fossil
The mass ratio of black alkene is 1.5:1.Other steps and parameter are same as Example 1.With graphene/core under the conditions of described in this embodiment
Flavine composite catalysis electrode is used as the obtained maximum output voltages of the MFC of negative electrode and peak power output respectively 0.51V
And 1100mW/m2。
Embodiment 3
The present embodiment is as different from Example 1：Step（2）Add 300 mg carboxylated graphenes, riboflavin and carboxyl fossil
The mass ratio of black alkene is 1:1.Other steps and parameter are same as Example 1.With graphene/core yellow under the conditions of described in this embodiment
Plain composite catalysis electrode as the obtained maximum output voltages of the MFC of negative electrode and peak power output be respectively 0.48V and
930mW/m2。
Embodiment 4
The present embodiment is as different from Example 1：Step（3）The temperature of microwave catalysis reaction is 80 DEG C.Other steps and parameter
It is same as Example 1.The MFC of negative electrode is used as under the conditions of described in this embodiment using graphene/riboflavin composite catalysis electrode
Obtained maximum output voltage and peak power output is respectively 0.43V and 695mW/m2。
Embodiment 5
The present embodiment is as different from Example 1：Step（3）The temperature of microwave catalysis reaction is 150 DEG C.Other steps and parameter
It is same as Example 1.The MFC of negative electrode is used as under the conditions of described in this embodiment using graphene/riboflavin composite catalysis electrode
Obtained maximum output voltage and peak power output is respectively 0.44V and 730mW/m2。
Embodiment 6
The present embodiment is as different from Example 1：Step（3）The power of microwave catalysis reaction is 500 W.Other steps and parameter
It is same as Example 1.The MFC of negative electrode is used as under the conditions of described in this embodiment using graphene/riboflavin composite catalysis electrode
Obtained maximum output voltage and peak power output is respectively 0.43V and 705mW/m2。
Embodiment 7
The present embodiment is as different from Example 1：Step（3）The power of microwave catalysis reaction is 900 W.Other steps and parameter
It is same as Example 1.The MFC of negative electrode is used as under the conditions of described in this embodiment using graphene/riboflavin composite catalysis electrode
Obtained maximum output voltage and peak power output is respectively 0.45V and 780mW/m2。
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implies relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".
The above-mentioned description to embodiment is understood that for ease of those skilled in the art and using this hair
It is bright.Person skilled in the art obviously easily can make various modifications to these implementations, and described herein one
As principle be applied in other embodiment without passing through performing creative labour.Therefore, the invention is not restricted to embodiment here,
Those skilled in the art are according to the announcement of the present invention, and the improvement made for the present invention and modification all should be in protections of the invention
Within the scope of.
Claims (6)
1. the preparation method of a kind of graphene/riboflavin composite, it is characterised in that comprise the following steps：
（1）Riboflavin is added in DMA, yellow solution is obtained after heating；
（2）To step（1）First is obtained in obtained yellow solution after addition carboxylated graphene and concentrated hydrochloric acid, heating water bath to mix
Compound；The mass ratio of riboflavin and carboxylated graphene is 1:1~2:1, the concentration of concentrated hydrochloric acid is 12mol/L, concentrated hydrochloric acid and N,
The volume ratio of N- dimethyl acetamides is 0.4:100；
（3）By step（2）The first obtained mixture is put into microwave reactor, carries out microwave catalysis reaction, is obtained second and is mixed
Compound；The reaction temperature of microwave catalysis reaction is 80 DEG C~150 DEG C, and the reaction time is 20min ± 2min, and reaction power is 500W
~900W；
（4）By step（3）The second obtained mixture carries out ultrasonically treated；
（5）By step（4）Repeatedly, vacuum is done for the second mixture DMA and deionized water rinsing after processing
Graphene/riboflavin composite is obtained after dry.
2. preparation method according to claim 1, it is characterised in that：Step（1）In, the heating-up temperature is 60 DEG C ± 5
℃。
3. preparation method according to claim 1, it is characterised in that：Step（2）In, the temperature of the heating water bath is 80
DEG C ± 5 DEG C, the time is 2h ± 0.2h.
4. preparation method according to claim 1, it is characterised in that：Step（3）In, the reaction of the microwave catalysis reaction
Temperature is 120 DEG C, and the reaction time is 20min, and reaction power is 700W.
5. preparation method according to claim 1, it is characterised in that：Step（4）In, the ultrasonically treated time is
1.5h ± 0.15h, ultrasound condition is low frequency.
6. preparation method according to claim 1, it is characterised in that：Step（5）In, the vacuum drying temperature is 60
DEG C ± 5 DEG C, the time is 48h ± 2h, and relative degree of vacuum is 0.05MPa~0.07MPa.
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Cited By (3)
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| CN112331864A (en) * | 2020-10-23 | 2021-02-05 | 同济大学 | Biological melanin/graphene composite material and preparation method and application thereof |
| CN112349917A (en) * | 2020-10-23 | 2021-02-09 | 同济大学 | Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof |
| CN112591741A (en) * | 2020-11-17 | 2021-04-02 | 同济大学 | Preparation method and application of carbon-based composite material |
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| CN112349917A (en) * | 2020-10-23 | 2021-02-09 | 同济大学 | Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof |
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