CN115403024A - Preparation method of asphalt derived carbon material and application of asphalt derived carbon material in enzyme biofuel cell - Google Patents

Preparation method of asphalt derived carbon material and application of asphalt derived carbon material in enzyme biofuel cell Download PDF

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CN115403024A
CN115403024A CN202210991789.6A CN202210991789A CN115403024A CN 115403024 A CN115403024 A CN 115403024A CN 202210991789 A CN202210991789 A CN 202210991789A CN 115403024 A CN115403024 A CN 115403024A
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enzyme
carbon material
electrode
asphalt
derived carbon
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张玉霞
李刚勇
邓红芬
许文苑
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Hunan Institute of Science and Technology
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Hunan Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/8605—Porous electrodes
    • 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
    • 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
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8689—Positive electrodes
    • 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 discloses a preparation method of an asphalt derived carbon material and application of the asphalt derived carbon material in an enzyme biofuel cell, wherein the asphalt derived carbon material is prepared by subjecting asphalt to K 2 FeO 4 And (3) catalyzing and carbonizing to obtain the catalyst. The invention designs and synthesizes the pitch-derived carbon material ADC as glucose/O 2 Electrode materials for EBFCs. The material has the characteristics of fluffy porosity and large specific surface area, is favorable for mass transfer and electric conduction, has the characteristic of reduced graphitization degree, and obviously enhances the enzyme immobilization, electrode stability and mass transfer, thereby improving the EBFCs performance. The results show that glucose/O equipped with pitch-derived carbon material ADC 2 EBFCs can output OCP up to 0.63V and 0.18mW cm 2 And has higher stability, which is mainly due to the porous structure and large specific surface area of the ADC, resulting in high enzyme loading. When the pitch-derived carbon material ADC is used as an enzyme support material for making biocathodes, it will contribute to the ORR of biocathodes, thereby improving EBFCs performance.

Description

Preparation method of asphalt-derived carbon material and application of asphalt-derived carbon material in enzyme biofuel cell
Technical Field
The invention relates to the technical field of enzyme biofuel cells, in particular to a preparation method of an asphalt derived carbon material and application of the asphalt derived carbon material in an enzyme biofuel cell.
Background
Enzyme biofuel cells (EBFCs) are a green energy conversion device for converting chemical energy of biomass fuel into electric energy by enzyme catalysis, have the characteristics of environmental friendliness and no pollution, and are expected to become one of the new approaches for developing renewable energy sources. The biofuel is oxidized at the anode to produce electrons that need to be transported to the cathode for reducing the oxidant. Since the active center of the enzyme is often located at the center of the enzyme protein, slow electron transfer between the enzyme and the electrode, low conductivity of the electrode, etc. tend to limit the performance of the enzyme biofuel cell. Therefore, carbonaceous materials having excellent conductivity, high specific surface area, electrochemical stability and high biocompatibility are often used as conductive nanowires to establish electrical communication between the active center of the enzyme and the electrode.
The asphalt has very complex components and structures, mostly belongs to polycyclic aromatic hydrocarbon and derivatives thereof, has the characteristics of high carbon content, high aromaticity and the like, is a high-quality precursor of a carbon material, has the advantages of wide source, high carbon yield, low cost and the like, and is particularly suitable for preparing products such as graphite materials, porous carbon, carbon fibers and the like. Meanwhile, the asphalt is selected as the raw material, the theme of world economy and environmental protection is met, waste is changed into valuable, and the loss rate of the raw material in the material manufacturing process is low. The asphaltene-derived carbon material has excellent physical and chemical properties such as large specific surface area, porous structure, excellent chemical stability, good electrical conductivity, high mechanical strength and the like, conforms to the advocation concept of green sustainable development, is concerned by the scientific community and is widely applied to the fields of material preparation, energy storage, biomedicine, biofuel cells and the like. Chou and the like take asphalt as a carbon source to prepare a silicon/carbon composite material and apply the silicon/carbon composite material to a lithium battery cathode, and the reversible capacity is 400mAhg -1 The capacity retention rate after 1000 cycles of charge and discharge was 71.3%. Mixing asphalt with asphalt by solution mixing methodThe problem of poor self-sintering property of the mesophase carbon microspheres during preparation of the graphite material by isostatic pressing, roasting and graphitization is effectively solved by mixing the mesophase carbon microspheres.
The research of 23428on the asphalt-based carbon material in the cathode of the lithium ion battery has been advanced, but the application of the asphalt-based carbon material in the biofuel battery is less researched. Due to the high aromaticity of asphalt molecules and strong pi-pi interaction among molecules in the carbonization process, the distance between carbon layers of the prepared soft carbon material is small, so that the soft carbon material is not beneficial to storing sodium ions with large radius, and in order to meet the requirement of continuous increase of higher electrocatalytic electrode performance, a novel mixed electrode material for immobilized enzymes needs to be developed for building EBFCs. The amorphous structure of the pitch-derived carbon material enables the defect to be larger, the layer surface has larger specific surface area and larger charge holding space, and the enzyme and the mediator can be adsorbed, so that more efficient electron transfer between the enzyme and the electrode can be realized.
Accordingly, one skilled in the art provides a method for preparing an asphalt-derived carbon material and its application in an enzyme biofuel cell to solve the problems set forth in the background art.
Disclosure of Invention
The invention aims to provide a preparation method of an asphalt-derived carbon material and application of the asphalt-derived carbon material in an enzyme biofuel cell, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing asphalt derived carbon material from asphalt through K 2 FeO 4 And (3) catalyzing and carbonizing to obtain the catalyst.
The preparation method comprises the following steps:
1)K 2 FeO 4 mixing with asphalt, and pulverizing to obtain mixed raw material powder;
2) Putting the mixed raw material powder into a container, and drying for 12 hours at the temperature of 60-70 ℃ in vacuum;
3) Cooling, grinding the above mixed raw material powder sample in a grinding pan, placing in a container, placing in the center of a horizontal tube furnace, and adding NH 3 Under stream or N2 streamHeating the tube furnace to 1200 ℃, and preserving heat for 2 hours;
4) After cooling the sample to room temperature, pour into a beaker and add the appropriate volume of H 2 SO 4 And performing oil bath at 70 ℃ for 24h, washing until the pH value is neutral, and drying at 60-70 ℃ in vacuum for 12h to obtain the product. The carbon material can be used as glucose/O 2 Electrode materials for EBFCs.
As a further scheme of the invention: in the step 1), the K 2 FeO 4 And asphalt in a mass ratio of 1/3-3:1, specifically 1.
As a still further scheme of the invention: the crushing mode is liquid adding grinding, and the particle size of the mixed raw material powder is smaller than 200 meshes.
As a still further scheme of the invention: in the step 2), the container is a common glass plate and is dried in a vacuum drying oven.
As a still further scheme of the invention: in the step 3), the heating rate is 1-10 ℃/min, and the heating rate can be 2 ℃/min.
As a still further scheme of the invention: in the step 4), the appropriate volume of H 2 SO 4 Specifically, it may be 2mol/L H of 5 times by volume 2 SO 4 . In the step 4), the method for washing the product to neutral pH comprises the following steps: the product was filtered through a sand-core funnel, washed thoroughly with deionized water to remove impurities, and then dried at 60 ℃.
The application of the pitch-derived carbon material in the enzyme biofuel cell comprises the following steps: the application is the application of the carbon material in the preparation of an enzyme biofuel cell, or the application is the application of the carbon material in the preparation of an electrode material for an biofuel cell; the biofuel cell may further be an enzymatic biofuel cell, in particular a glucose/oxygen biofuel cell; the carbon material acts as a carrier for immobilized enzymes in the glucose/oxygen biofuel cell.
An enzyme electrode comprises a substrate electrode, a carbon material layer and an enzyme layer in sequence; further, the enzyme electrode also comprises Nafi coated on the surface of the enzyme layerCoating on; the substrate electrode can be a Glassy Carbon Electrode (GCE), foamed nickel, carbon paper, carbon cloth or carbon felt; in the carbon composite material layer, the content of the carbon composite material on each square centimeter of the substrate electrode is 5.92-11.84 mg-cm -2 (ii) a The enzyme in the enzyme layer may specifically be glucose oxidase (GOx) or Bilirubin Oxidase (BOD); when the enzyme layer is glucose oxidase (GOx), the enzyme electrode can be used as an anode in an enzyme biofuel cell electrode; when the enzyme layer is Bilirubin Oxidase (BOD), the enzyme electrode may serve as a cathode in an enzyme biofuel cell electrode; the Nafion coating is formed by dripping Nafion solution on the surface of the enzyme layer and drying.
An enzyme biofuel cell. The enzyme biofuel cell includes the enzyme electrode described above, and the inventors of the present invention developed a convenient catalytic pyrolysis synthesis strategy to synthesize pitch-derived carbon material ADC.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention designs and synthesizes the pitch-derived carbon material ADC as glucose/O 2 Electrode materials for EBFCs. The material has the characteristics of fluffy and porous property and large specific surface area, is favorable for mass transfer and electric conduction, has the characteristic of reduced graphitization degree, and obviously enhances the enzyme immobilization, the electrode stability and the mass transfer, thereby improving the EBFCs performance. The results show that glucose/O of ADC equipped with pitch-derived carbon material 2 EBFCs can output OCP up to 0.63V and 0.18mW cm 2 Has high stability, which is mainly due to the porous structure and large specific surface area of the ADC, which brings high enzyme load. The amorphous structure enables the defects to be larger, has larger specific surface area and larger charge holding space on the layer surface, and can adsorb enzyme and mediator so as to promote more efficient electron transfer between the enzyme and the electrode. When the pitch-derived carbon material ADC is used as an enzyme support material for making biocathodes, it will contribute to the ORR of biocathodes, thereby improving EBFCs performance.
2. The carbon material synthesized by the invention is asphalt K 2 FeO 4 Asphalt-based carbon nano composite formed by catalytic pyrolysisComposite material and characterized as electrode material for fixing GOx and BOD to construct glucose/O 2 EBFCs. The pitch-derived carbon material may facilitate electron transfer from the active center of the enzyme to the electrode surface. Most importantly, the rough surface and the porous nano structure endow the asphalt-derived carbon material with an excellent enzyme capture function, and the enzyme can be adsorbed on the surface of the material and can be encapsulated in the pores of the material. Thus, the assembled EBFCs exhibit high OCP up to 0.63V, with a maximum power density of 0.18mW cm at 0.29V -2 Pitch-derived carbon materials are therefore promising candidates for capturing other biocatalysts for a wide range of biotechnological applications.
Drawings
Fig. 1 is an XRD pattern of pitch-derived carbon material ADC for a method of preparing pitch-derived carbon material and its application in enzyme biofuel cell.
Fig. 2 is a FTIR plot of pitch-derived carbon material ADC in a process for preparing pitch-derived carbon material and its application in enzymatic biofuel cells.
Fig. 3 is a pore size distribution diagram of a pitch-derived carbon material ADC in a method of preparing the pitch-derived carbon material and its application in an enzyme biofuel cell.
Fig. 4 is a nitrogen isothermal adsorption and desorption curve diagram of a pitch-derived carbon material ADC in a preparation method of the pitch-derived carbon material and application of the pitch-derived carbon material in an enzyme biofuel cell.
Fig. 5 is a scanning electron microscope image of a pitch-derived carbon material ADC in a method for preparing a pitch-derived carbon material and its application in an enzyme biofuel cell.
Fig. 6 is a CV curve diagram of a pitch-derived carbon material loaded on a glassy carbon electrode by an ADC (analog to digital converter) in a preparation method of the pitch-derived carbon material and an application of the pitch-derived carbon material in an enzyme biofuel cell.
Fig. 7 (a) is a schematic CV diagram of a preparation method of a pitch-derived carbon material and a pitch-derived carbon material ADC loaded on a glassy carbon electrode in an application of the pitch-derived carbon material in an enzyme biofuel cell;
FIG. 7 (b) is an EIS diagram of a preparation method of a pitch-derived carbon material and ADC-3/TTF/GOx loaded on a glassy carbon electrode in the application of the pitch-derived carbon material in an enzyme biofuel cell.
FIG. 8 (a) is a graph showing CV curves for ADC-0, ADC-3, ADC-0/TTF/GOx and ADC-0/TTF/GOx electrodes in 0.5M PBS (pH 7.0) for a pitch-derived carbon material and its use in enzyme biofuel cells;
FIG. 8 (b) is a graph showing the CV curves of ADC-0/TTF/GOx and ADC-0/TTF/GOx electrodes in 0.5M PBS (pH 7.0) with or without 0.1M glucose in the enzyme biofuel cell application.
FIG. 9 (a) is a CV curve of an ADC/TTF/GOx electrode in 0.5M PBS (pH 7.0) at different sweep rates for a method of making pitch-derived carbon material and its application in enzyme biofuel cells;
FIG. 9 (b) is a graph of Ep versus Ln v for a process for the preparation of pitch derived carbon material and its use in enzyme biofuel cells;
FIG. 9 (c) is a process for preparing an asphalt-derived carbon material and its current density and v in the application of enzyme biofuel cells 1/2 A relationship diagram of (a);
FIG. 9 (d) is a graph of current density versus glucose concentration for a pitch derived carbon material and its use in an enzyme biofuel cell;
FIG. 10 is a schematic diagram of the current response of an ADC/TTF/GOx modified glassy carbon electrode with continuous addition of 5mM glucose, 0.2mM Uric Acid (UA), 0.2mM acetaminophen (APAP), 0.2mM Dopamine (DA) and 5mM glucose in the preparation method of an asphalt derived carbon material and its application in an enzyme biofuel cell.
FIG. 11 (a) is a graph of the power density of a biocolloid single cell for a process for the preparation of pitch-derived carbon material and its application in enzyme biofuel cells;
fig. 11 (b) is a diagram of a preparation method of an asphalt-derived carbon material and an LED bulb lighted by four bio-gel batteries connected in series in the application of the asphalt-derived carbon material in an enzyme biofuel cell.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1 to 11, in an embodiment of the present invention, a method for preparing an asphalt-derived carbon material from asphalt via K 2 FeO 4 And (3) catalyzing and carbonizing to obtain the catalyst.
The preparation method comprises the following steps:
1)K 2 FeO 4 mixing with asphalt, and pulverizing to obtain mixed raw material powder;
2) Putting the mixed raw material powder into a container, and drying for 12 hours at the temperature of 60-70 ℃ in vacuum;
3) Cooling, grinding the above mixed raw material powder sample in a grinding pan, placing in a container, placing in the center of a horizontal tube furnace, and adding NH 3 Heating the tube furnace to 1200 ℃ under the flow or N2 flow, and preserving heat for 2h;
4) After cooling the sample to room temperature, pour into a beaker and add the appropriate volume of H 2 SO 4 And carrying out oil bath at 70 ℃ for 24h, washing until the pH is neutral, and drying at 60-70 ℃ in vacuum for 12h to obtain the water-soluble organic fertilizer. The carbon material can be used as glucose/O 2 Electrode materials for EBFCs.
In step 1) of the above process, said K 2 FeO 4 And asphalt in a mass ratio of 1/3-3:1, specifically 1.
The crushing mode is liquid adding grinding, and the particle size of the mixed raw material powder is less than 200 meshes.
In the step 2), the container is a common glass plate and is dried in a vacuum drying oven.
In the step 3), the heating rate is 1-10 ℃/min, and the heating rate can be 2 ℃/min.
In the step 4), the appropriate volume of H 2 SO 4 Specifically, it may be 2mol/L H of 5 times by volume 2 SO 4 。
In the step 4), the method for washing the product until the pH value is neutral comprises the following steps: the product was filtered through a sand-core funnel, washed thoroughly with deionized water to remove impurities, and then dried at 60 ℃.
The application of the pitch-derived carbon material in the enzyme biofuel cell comprises the following steps:
the application refers to the application of the carbon material in the preparation of an enzyme biofuel cell, or the application refers to the application of the carbon material in the preparation of an electrode material for the biofuel cell; the biofuel cell may further be an enzymatic biofuel cell, in particular a glucose/oxygen biofuel cell; the carbon material serves as a carrier for immobilizing enzymes in the glucose/oxygen biofuel cell.
The invention also protects an enzyme electrode. The enzyme electrode sequentially comprises a substrate electrode, a carbon material layer and an enzyme layer; further, the enzyme electrode also comprises a Nafion coating coated on the surface of the enzyme layer; the substrate electrode can be a Glassy Carbon Electrode (GCE), foamed nickel, carbon paper, carbon cloth or carbon felt; in the carbon composite material layer, the content of the carbon composite material on the base electrode per square centimeter is 5.92-11.84 mg-cm -2 (ii) a The enzyme in the enzyme layer can be glucose oxidase (GOx) or Bilirubin Oxidase (BOD); when the enzyme layer is glucose oxidase (GOx), the enzyme electrode can be used as an anode in an enzyme biofuel cell electrode; when the enzyme layer is Bilirubin Oxidase (BOD), the enzyme electrode may serve as a cathode in an enzyme biofuel cell electrode; the Nafion coating is formed by dripping Nafion solution on the surface of the enzyme layer and drying.
The invention also protects an enzyme biofuel cell. The enzyme biofuel cell comprises the enzyme electrode. The inventors of the present invention developed a convenient catalytic pyrolysis synthesis strategy to synthesize pitch-derived carbon material ADC.
The invention designs and synthesizes the pitch-derived carbon material ADC as glucose/O 2 Electrode materials for EBFCs. The material has the characteristics of fluffy and porous property, large specific surface area, contribution to mass transfer and electric conduction, and reduced graphitization degree, and is remarkableThe immobilization of enzyme, the stability of the electrode and mass transfer are enhanced, thereby improving the performance of EBFCs. The results show that glucose/O equipped with pitch-derived carbon material ADC 2 EBFCs can output OCP up to 0.63V and 0.18mW cm 2 And has higher stability, which is mainly due to the porous structure and large specific surface area of the ADC, resulting in high enzyme loading. The amorphous structure enables the defects to be larger, has larger specific surface area and larger charge holding space on the layer surface, and can adsorb enzyme and mediator so as to promote more efficient electron transfer between the enzyme and the electrode. When the pitch-derived carbon material ADC is used as an enzyme support material for making biocathodes, it will contribute to the ORR of biocathodes, thereby improving EBFCs performance.
Synthesis and characterization of pitch-derived carbon material ADC:
1. synthesis of pitch-derived carbon material ADC
0.5g of K 2 FeO 4 And 3ml of H 2 After the O was mixed well in the beaker, 1g of pitch was ground in a mortar and pestle for at least 20 minutes to ensure good mixing of the precursors. Obtaining mixed raw material powder; putting the mixed raw material powder into a glass plate, and drying the mixed raw material powder in a vacuum drying oven at the temperature of between 60 and 70 ℃ for 12 hours to completely dry the mixed raw material powder; the above mixed raw material powder sample was again charged into a grinding pot and ground to obtain a fine powder (particle size less than 200 mesh). After the regrinding, the powder is loaded into a graphite crucible, placed in the center of a horizontal tube furnace and then in NH 3 Flow or N 2 Flowing down at 2 deg.C for min -1 The tube furnace is heated to 1200 ℃ at the heating rate of (1), and the temperature is kept for 2h at 1200 ℃; cooling the sample to room temperature, pouring the product into a beaker, adding 2M H with 5 times of volume 2 SO 4 And carrying out oil bath at 70 ℃ for 24h, thoroughly washing the product with deionized water until the pH is neutral, and then drying at 60-70 ℃ for 12h in vacuum to obtain the pitch-derived carbon material ADC.
2. Characterization of pitch-derived carbon material ADC
The pitch-derived carbon material ADC is obtained by using pitch and K 2 FeO 4 Prepared by a convenient catalytic pyrolysis process. Schematic of pitch-derived carbon Material ADCAnd (4) synthesizing. Mixing asphalt with K 2 FeO 4 Mixed together thoroughly to form a fine powder. And then heating the precursor at 1200 ℃ for 2 hours to obtain the pitch derived carbon material. The structural property and the morphology of the synthesized asphalt derived carbon material ADC are researched by using an XRD, an FTIR, a full-automatic specific surface area and micropore physical adsorption analyzer and an electron microscope. In the XRD pattern (FIG. 1), with K 2 FeO 4 When the mass ratio of (002) to (002) is 1. Corresponding SEM images of pitch-derived carbon materials are shown in FIG. 5, where pitch-derived carbon materials are at N 2 In the atmosphere, with K 2 FO 4 The mass ratio is increased, the asphalt derived carbon material has a fluffy porous structure, the specific surface area is increased, mass transfer is facilitated, and the graphitization degree is reduced. NH 3 In an atmosphere, the material level tends to be randomly flexible. The local graphitization will impart excellent electrical conductivity to the pitch-based carbon nanocomposite with fast electron transfer kinetics. Furthermore, the porous and open structure allows the enzymes to easily penetrate inside the bitumen derived material ADC, and the rough surface allows a large amount of enzymes to be adsorbed onto its surface.
Preparation and electrochemical measurement of a working electrode based on an asphalt-derived carbon material ADC:
1. preparation of working electrode based on asphalt derived carbon material ADC
The working electrode was an enzyme/pitch-derived carbon material ADC modified glassy carbon electrode (GCE, 3mm diameter). Before modification, GCE was polished on a polishing cloth with alumina slurries (0.3 μm and 0.03 μm), then sonicated in double distilled water and ethanol for 15 seconds in sequence, and then dried at room temperature. A simple drop casting method is used to manufacture the working electrode. 10 μ L of the asphalt-derived carbon material ADC suspension (10 mg mL) -1 Dispersed in N, N-dimethylformamide) and 2ul of tetrathiafulvalene (TTF) mediator solution (0.02M, solvent acetonitrile) were mixed well, 2ul of which was cast onto the surface of the pretreated GCE and dried in air. Then, 5 μ L of GOx solution was cast onto the surface of the pitch-derived carbon material ADC-modified GCE, and the electrode was brought to 4 deg.CThe refrigerator of (1) was kept for 4 hours. Finally, 3 μ L Nafion solution (5 ‰) was dropped on the surface of GCE modified with GOx/pitch-derived carbon material ADC, and the electrodes were stored in a refrigerator at 4 ℃ for 2h to obtain bioanode (expressed as ADC/TTF/GOx).
For biocathode preparation, 10. Mu.L of the asphalt-derived carbon material ADC suspension (10 mg mL) -1 Dispersed in N, N-dimethylformamide) and 2ul 2,2' -azidobis (3-ethylbenzothiazoline-6-sulfonic Acid) (ABTS) mediator solution (0.02M, solvent water) were mixed well and 2ul was cast on the surface of the pretreated GCE and dried in air. Then, 5 μ L BOD solution was cast on the surface of the pitch-derived carbon material ADC-modified GCE, and the electrodes were stored in a refrigerator at 4 ℃ for 4h. Finally, 3 μ L Nafion solution (5 ‰) was dropped on the surface of the GCE modified with BOD/pitch derived carbon material ADC, and the electrodes were kept in a refrigerator at 4 ℃ for 2h to obtain a biological cathode (expressed as ADC/ABTS/BOD).
For control experiments, ADC/GOx, ADC/BOD were prepared in a similar manner.
2. Electrochemical measurement of working electrode
Electrochemical experiments were performed on a CHI660E electrochemical workstation in a three electrode system, where GOx/BOD/ADC/GCE was used as the working electrode, ag/AgCl in 3M KCl was used as the reference electrode, pt foil (1 cm) 2 ) Serving as a counter electrode. Will N 2 Saturated 0.5M PBS (pH 7.0) was used as supporting electrolyte. Use of a solution comprising 5mM 2 [ Fe (CN) 6 ] 3-/4- Was used as a working electrode with bare GCE and BOD/pitch derived carbon material ADC modified GCE at a frequency of 0.01Hz to 100kHz at an AC applied potential of 1mV, and Electrochemical Impedance Spectroscopy (EIS) data was obtained. Linear Sweep Voltammetry (LSV) experiments were performed at N 2 In saturated 0.5M PBS (pH 7.0) containing varying concentrations of glucose at a scan rate of 10mV s -1 . All tests were performed at room temperature.
3. Electrochemical performance
Electrochemical tests were performed on enzyme-modified electrodes and assembled fuel cells using cyclic voltammetry and constant current discharge with 0.1M KCl as the supporting electrolyte solution, 0.1M KCl,5mM Fe[(CN) 6 ] 3/4- ) For electrochemically active probes, CV tests were performed on GCE and ADC modified GCE under a three-electrode system, as shown in figure 6. A pair of reversible redox peaks corresponding to Fe [ (CN) 6 ] 3/4- ) Reversible redox reaction of the couple. The ADC modified GCE has higher faraday current and smaller redox peak separation than GCE, indicating that ADC possesses higher electroactive area and excellent electron transfer kinetics. FIG. 7 (b) is an EIS curve of GCE and ADC-modified GCE. The semi-circle of the high and medium frequency region represents the charge transfer resistance. It is clearly observed that there is a half circle in the EIS curve of the GCE electrode. The EIS curve of the ADC modified GCE in the high-frequency region and the medium-frequency region does not have an obvious semicircle, which indicates that the ADC modified GCE is more superior to the GCE in the aspect of charge transfer dynamics.
FIG. 8 (a) is a CV curve of various modified electrodes in 0.1M PBS saturated with nitrogen (pH7.0). As shown in the figure, a pair of redox peaks appears when ADC, TTF and GOx are simultaneously modified on GCE, the apparent potential of the redox peak is 0.34V (vs. Ag/AgCl), and the redox peak is similar to the GOx active center FAD/FADH reported in the literature 2 The apparent potentials of the redox couples are much different, indicating that the ADC material cannot achieve DET of GOx as a support material for GOx, further illustrating the necessity of mediator-mediated electron transfer. FIG. 8 (b) is a CV curve after glucose addition, showing a pair of redox peaks when ADC, TTF and GOx are simultaneously modified on GCE, demonstrating that the enzyme successfully catalyzes glucose, and that the specific surface of the modified material adsorbs more TTF to mediate electrons, and has a larger oxidation current, which also indicates the necessity of mediator-mediated electron transfer.
FIG. 9 investigates cyclic voltammograms of ADC/TTF/GOx at different scan rates to evaluate electron transfer kinetics. FIG. 9 (a) shows ADC/TTF/GOx at from 50 to 500mV s -1 CV curve at different scan rates. FIG. 9 (b) the linear relationship between redox peak current and scan rate indicates that GOx in ADC/TTF/GOx is a quasi-reversible surface-limited process. At high scan rates, the peak potential is linear with the nanopipel logarithm of the scan rate (fig. 9 c). FIG. 9 (d) is a graph for exploring the kinetics of catalytic current as a function of glucose concentration and maximal catalysisThe results show that as the glucose concentration increases, the catalytic current also increases.
4. Specific detection of bioelectrocatalytic properties
FIG. 10 investigates the selectivity and interference rejection performance of the resulting ADC/TTF/GOx bioanode. Chronoamperometric response of glucose, UA, APAP, DA, continuously added at 0.1V (vs. Ag/AgCl) working potential in 0.5M PBS (pH 7.0). It is known from the figure that the addition of glucose leads to a clearly detectable oxidation current on the ADC/TTF/GOx bioanode, that the addition of interfering substances UA, APAP, DA (respectively at physiological levels of 0.2 mM) does not lead to a detectable change in the current signal, and that the subsequent addition of glucose leads to a further pronounced oxidation current. The results clearly show that the prepared ADC/TTF/GOx biological anode has extremely high selectivity and anti-interference performance on substrate glucose, so that in practical application, a high-specificity reaction on glucose can be obtained without using a permselective membrane.
Preparation of a biological anode and a biological cathode:
carbon paper is used as a current collector for the preparation of bioanodes and biocathodes due to its superior electrical conductivity, lower toxicity and 3D porous structure that provides more transport conditions. Before use, the carbon paper was sonicated in acetone and 3M HCl for 30min, respectively, to remove organic impurities and oxide layers. The cutting area is 3 x 3cm 2 . To prepare the bioanode, 200 μ L of pitch-derived carbon material ADC suspension (10 mg mL) -1 Dispersed in N, N-dimethylformamide) and 40ul of tetrathiafulvalene (TTF) mediator solution (0.02M, solvent acetonitrile) were mixed well, 225ul of which was cast onto the surface of carbon paper and dried in air (denoted as pitch-based carbon nanocomposite/carbon paper). Then, 113 μ L of GOx solution was poured onto the surface of the pitch derived carbon material ADC foam and the electrodes were stored in a refrigerator at 4 ℃ for 4h (expressed as GOx/ADC/nickel foam). Finally, 135. Mu.L of Nafion solution (5 ‰) was dropped on the surface of GOx/ADC/carbon paper, and the electrode was stored in a refrigerator at 4 ℃ for 1 hour and expressed as (Nafion/GOx/ADC/carbon paper). The amount of GOx immobilized on the nickel foam was about 1.6mg.cm -2 . To prepare a biocathode, similarly, 80 μ L of ADC/carbon paper supernatant (5 mg) was addedmL -1 Dispersed in deionized water) was cast onto the surface of the carbon paper and dried in air (denoted ADC/carbon paper). Then, 100 μ L BOD solution was slipped over the ADC/nickel foam surface and the electrodes were stored in a refrigerator at 4 ℃ for 4h (expressed as BOD/ADC/carbon paper). Finally, 80. Mu.L of Nafion solution (5 ‰) was dropped on the BOD/ADC/carbon paper surface and the electrodes were stored in a refrigerator at 4 ℃ for 1h (expressed as Nafion/BOD/ADC/carbon paper). The amount of BOD immobilized on the carbon paper was about 2mg -2 。
Design and evaluation of glucose/oxygen EBFCs:
glucose/O 2 EBFCs were assembled using Nafion/GOx/ADC/carbon paper as the bioanode and Nafion/BOD/ADC/carbon paper as the biocathode laminated on both sides of a block of hydrogel electrolyte. The current is led out from the nickel conducting sheet by using conducting adhesive behind the cathode carbon paper and the anode carbon paper, a piece of foam net is superposed behind the cathode carbon paper to be used as a gas diffusion layer, then the cathode and the anode are fixed by using a glass slide and a dovetail clamp, and finally the cathode and the anode are clamped on the nickel sheet by using conducting wires in sequence to assemble a series circuit. And acrylamide monomer (AAM, 1.422 g) and N, N-methylene benzene (acrylamide) (MBA, 0.001 g) crosslinker were added to 5mL phosphate buffer solution (0.5M, pH 7.0) with continuous stirring prior to use. After adding potassium persulfate initiator (APS, 0.257 g) to the above solution, the solution was poured into a self-made mold, placed in an oven, polymerized at 50 ℃ for 30min, and the resulting hydrogel sheet was immersed in a phosphate buffer solution containing 100mM glucose for 24h to allow glucose to penetrate into the hydrogel sheet.
Testing of glucose/O Using CHI660E electrochemical workstation 2 Open Circuit Potential (OCP) and polarization curve (LSV) of EBFCs.
glucose/O 2 Performance of EBFCs: the oxidation of glucose can be successfully realized on GOx/ADC/GCE through a direct bioelectrocatalysis reaction, so that the OCP of EBFCs is expected to be improved. In addition, BOD immobilized on pitch-derived carbon material in the presence of ABTS exhibits excellent O 2 Reduction performance. These advantages make the pitch-derived carbon material a building high performance glucose/O 2 As required by the EBFCs. Therefore, GOx/ADC/carbon paper biological anode and BOD/ADC/carbon paper biological cathode are addedPressing two sides of a hydrogel electrolyte to assemble glucose/O 2 EBFCs, as shown in FIG. 11. After standing for 1h, single glucose/O 2 The OCP of EBFCs can be as high as 0.63V.4 glucose/O in series 2 EBFCs can power yellow LED lamps. Single glucose/O 2 The maximum power density of EBFCs at 0.29V is 0.18mW cm -2 Higher than most of the glucose/O reported previously 2 EBFCs. In contrast, the performance of the fuel cell consisting of the ADC/carbon paper electrode without enzyme was negligible, indicating that the cell energy was derived from enzyme catalysis.
In summary, the invention synthesizes a novel carbon material which is asphalt warp K 2 FeO 4 Pitch-based carbon nanocomposites formed by catalytic pyrolysis and characterized as electrode materials for immobilization of GOx and BOD for glucose/O 2 EBFCs. The pitch derived carbon material may facilitate electron transfer from the active center of the enzyme to the electrode surface. Most importantly, the rough surface and the porous nano structure endow the asphalt derived carbon material with excellent enzyme capture function, and the enzyme can be adsorbed on the surface of the material and can be encapsulated in the pores of the material. Thus, the assembled EBFCs exhibit high OCP up to 0.63V, with a maximum power density of 0.18mW cm at 0.29V -2 Pitch-derived carbon materials are therefore promising candidates for capturing other biocatalysts for a wide range of biotechnological applications.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.

Claims (8)

1. The preparation method of the asphalt-derived carbon material is characterized in that the asphalt-derived carbon material is prepared by subjecting asphalt to K treatment 2 FeO 4 And (3) catalyzing and carbonizing to obtain the catalyst.
The preparation method comprises the following steps:
1)K 2 FeO 4 mixing with asphalt, and pulverizing to obtain mixed raw material powder;
2) Putting the mixed raw material powder into a container, and drying for 12 hours at the temperature of 60-70 ℃ in vacuum;
3) Cooling, grinding the above mixed raw material powder sample in a grinding pan, placing in a container, placing in the center of a horizontal tube furnace, and adding NH 3 Heating the tube furnace to 1200 ℃ under the flow or N2 flow, and preserving the heat for 2h;
4) After cooling the sample to room temperature, pour into a beaker and add the appropriate volume of H 2 SO 4 And carrying out oil bath at 70 ℃ for 24h, washing until the pH is neutral, and drying at 60-70 ℃ in vacuum for 12h to obtain the water-soluble organic fertilizer. The carbon material can be used as glucose/O 2 Electrode materials for EBFCs.
2. The method for preparing an asphalt-derived carbon material according to claim 1, wherein in the step 1), the K is 2 FeO 4 And asphalt in a mass ratio of 1/3-3:1, and specifically can be 1.
3. The method for preparing an asphalt-derived carbon material according to claim 1, wherein in step 2), the container is a common glass plate, and is dried in a vacuum drying oven.
4. The method for preparing an asphalt-derived carbon material according to claim 1, wherein in the step 3), the heating rate is 1-10 ℃/min, and the heating rate is 2 ℃/min.
5. The method for preparing an asphalt derived carbon material according to claim 1, wherein said appropriate volume of H in step 4) is 2 SO 4 Specifically, it may be 2mol/L H of 5 times by volume 2 SO 4 (ii) a In the step 4), the method for washing the product to neutral pH comprises the following steps: the product was filtered through a sand-core funnel, washed thoroughly with deionized water to remove impurities, and then dried at 60 ℃.
6. The application of the pitch-derived carbon material in the enzyme biofuel cell as claimed in claim 1, wherein the application is the application of the carbon material in the preparation of the enzyme biofuel cell or the application is the application of the carbon material in the preparation of an electrode material for the biofuel cell; the biofuel cell may further be an enzymatic biofuel cell, in particular a glucose/oxygen biofuel cell; the carbon material acts as a carrier for immobilized enzymes in the glucose/oxygen biofuel cell.
7. The enzyme electrode is characterized by comprising a substrate electrode, a carbon material layer and an enzyme layer in sequence; further, the enzyme electrode also comprises a Nafion coating coated on the surface of the enzyme layer; the substrate electrode can be a Glassy Carbon Electrode (GCE), foamed nickel, carbon paper, carbon cloth or carbon felt; in the carbon composite material layer, the content of the carbon composite material on the base electrode per square centimeter is 5.92-11.84 mg-cm -2 (ii) a The enzyme in the enzyme layer may specifically be glucose oxidase (GOx) or Bilirubin Oxidase (BOD); when the enzyme layer is glucose oxidase (GOx), the enzyme electrode can be used as an anode in an enzyme biofuel cell electrode; when the enzyme layer is Bilirubin Oxidase (BOD), the enzyme electrode may serve as a cathode in an enzyme biofuel cell electrode; the Nafion coating is formed by dripping Nafion solution on the surface of the enzyme layer and drying.
8. An enzyme biofuel cell, characterized in that the enzyme biofuel cell comprises the above enzyme electrode.
CN202210991789.6A 2022-08-17 2022-08-17 Preparation method of asphalt derived carbon material and application of asphalt derived carbon material in enzyme biofuel cell Pending CN115403024A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010516017A (en) * 2007-01-05 2010-05-13 アケルミン・インコーポレイテッド Bioanode and biocathode stack assembly
US20140080011A1 (en) * 2011-05-23 2014-03-20 Korea University Research And Business Foundation Manufacturing method for catalyst electrode, catalyst electrode manufactured by means of method, and battery comprising same
JP2017215210A (en) * 2016-05-31 2017-12-07 アイシン精機株式会社 Enzyme electrode with gluconate oxidation catalytic ability, fabrication method of enzyme electrode, bio battery, and bio sensor
CN107902654A (en) * 2017-10-23 2018-04-13 东华大学 A kind of coal tar asphalt is modified the preparation method and application of high-ratio surface porous carbon

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010516017A (en) * 2007-01-05 2010-05-13 アケルミン・インコーポレイテッド Bioanode and biocathode stack assembly
US20140080011A1 (en) * 2011-05-23 2014-03-20 Korea University Research And Business Foundation Manufacturing method for catalyst electrode, catalyst electrode manufactured by means of method, and battery comprising same
JP2017215210A (en) * 2016-05-31 2017-12-07 アイシン精機株式会社 Enzyme electrode with gluconate oxidation catalytic ability, fabrication method of enzyme electrode, bio battery, and bio sensor
CN107902654A (en) * 2017-10-23 2018-04-13 东华大学 A kind of coal tar asphalt is modified the preparation method and application of high-ratio surface porous carbon

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