CN114927735A - Enzyme biofuel cell for generating electricity by utilizing living plants - Google Patents
Enzyme biofuel cell for generating electricity by utilizing living plants 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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
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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
- H01M4/88—Processes of manufacture
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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
- H01M4/96—Carbon-based electrodes
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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 invention discloses an enzyme biofuel cell for generating electricity by utilizing living plants. The enzyme biofuel cell comprises a biological anode, a biological cathode and electrolyte agarose hydrogel; the biological anode comprises carbon cloth, and a three-dimensional nitrogen-doped carbon layer, a 1, 4-naphthoquinone layer and a glucose dehydrogenase layer which are sequentially superposed on the carbon cloth; the biological cathode comprises a carbon cloth, and a three-dimensional nitrogen-doped carbon layer and a bilirubin oxidase layer which are sequentially superposed on the carbon cloth; the agarose hydrogel was prepared from a 1% agarose solution. The invention can also connect the fuel cells in series and/or parallel to form a plant-activated enzyme biofuel stack. In generating electricity, each enzyme biofuel cell device is inserted into a single plant or into separate split parts cut from a plant. The invention can realize reasonable configuration of the battery, thereby exerting the effect of each configuration to the maximum extent and supplying power to different devices according to requirements.
Description
Technical Field
The invention belongs to the field of biofuel cells, and particularly relates to an enzyme biofuel cell for generating electricity by utilizing living plants.
Background
The rapid increase in the demand for power to portable microelectronic devices has provided a strong impetus for the development of energy technology, particularly under challenging conditions (e.g., limited resources and remote locations). Although conventional systems have been developed in this regard, they are bulky, have low safety, are scarce and harmful in chemical agents, and require frequent charging, greatly hindering further development in practical applications. Therefore, it is of great interest to develop a sustainable energy technology that is renewable, readily available, has a high energy density, and is highly safe. Enzymatic biofuel cells (EBFC) are usually the system of choice because the high reaction selectivity of oxidoreductases brings unique advantages, including high energy density and the possibility of generating electricity from biological fluids abundant in living organisms without purification.
Plants, as a highly productive organism, are distributed worldwide and even in remote fields, and therefore biological fluids in living plants are considered as a ready source of energy of choice (fig. 1 a). Given that glucose produced by metabolism is one of the most important energy sources for living organisms, glucose/oxygen EBFCs, which extract electrical energy from biological fluids abundant in living organisms, raise a continuing concern for energy harvesting challenges for electronic devices. For example, Katz and his colleagues reported an orange power generation and successful activation of the radio transmitter with the help of a charge pump [1 ].
Unfortunately, while some microelectronic devices may operate under relatively low electrical operating conditions, the operating voltage required by others is a few volts or milliwatts of power [2 ]. For example, measurements using an external variable power supply result in a minimum voltage of 0.7V 3 required for operation of the watch. In addition, a one-time ovulation test requires a minimum voltage of 3V and a power of 1.7mW for activation [4 ]. Therefore, certain types of microelectronic devices powered by plant-activated EBFCs require great attention not only to power factors but also to voltage regulation. Unfortunately, the Open Circuit Voltage (OCV) produced by EBFC is thermodynamically limited by the redox potential of glucose oxidation and oxygen reduction [5 ]. To increase the voltage, researchers often use additional charge pumps to increase the dc voltage [6], but at the cost of more current consumed by the charge pump [7 ]. Furthermore, the power and current output of EBFC cannot be increased simply by increasing the geometry of the electrode, since uniform immobilization of the enzyme across the entire electrode surface becomes a problem. The effects of internal resistance of the electrodes, solution resistance and mass transfer cause current distribution that cannot be neglected [8 ]. It is important to explore a versatile and novel strategy for increasing the output current and/or voltage as needed without incurring additional energy losses in order to meet the operating conditions of different microelectronic devices.
Reference documents:
[1]P.Bollella,I.Lee,D.Blaauw,E.Katz,"A microelectronic sensor device powered by a small implantable biofuel cell",no.2020
[2]L.Halámková,J.Halámek,V.Bocharova,et al.,"Implanted Biofuel Cell Operating in a Living Snail",Journal of the American Chemical Society,Vol.134,no.11,pp 5040-5043,2012
[3]V.Flexer,N.Mano,"From Dynamic Measurements of Photosynthesis in a Living Plant to Sunlight Transformation into Electricity",Analytical Chemistry,Vol.82,no.4,pp 1444-1449,2010
[4]Y.Holade,K.MacVittie,T.Conlon,et al.,"Wireless Information Transmission System Powered by an Abiotic Biofuel Cell Implanted in an Orange",Electroanalysis,Vol.27,no.2,pp 276-280,2015
[5]V.Andoralov,M.Falk,D.B.Suyatin,et al.,"Biofuel Cell Based on Microscale Nanostructured Electrodes with Inductive Coupling to Rat Brain Neurons",Scientific Reports,Vol.3,no.1,pp 3270,2013.
[6]T.Miyake,K.Haneda,N.Nagai,et al.,"Enzymatic biofuel cells designed for direct power generation from biofluids in living organisms",Energy&Environmental Science,Vol.4,no.12,pp 5008-5012,2011
[7]A.Szczupak,J.Halámek,L.Halámková,et al.,"Living battery-biofuel cells operating in vivo in clams",Energy&Environmental Science,Vol.5,no.10,pp 8891-8895,2012
[8]K.MacVittie,J.Halámek,L.Halámková,et al.,"From“cyborg”lobsters to a pacemaker powered by implantable biofuel cells",Energy&Environmental Science,Vol.6,no.1,pp 81-86,2013.
disclosure of Invention
The present invention proposes a new EBFC stacking strategy based on a single plant, with the hope of powering various devices without the help of additional electronics (fig. 1 b). As proof of concept, the device was first designed and inserted into natural plants like apple, pear, cactus and aloe to generate electricity (fig. 1 c). To improve electron transfer, three-dimensional nitrogen-doped carbon assembled from interwoven nanofibers (3D-NCAIN) was synthesized and used as an electrode substrate (fig. 1D). Various configurations consisting of series, parallel and series-parallel connections were investigated to modulate the energy harvesting of EBFC in live fruits. The invention provides the possibility of stacking the cells easily in a series or parallel configuration, with only one plant (e.g., pear) being required to achieve on-demand power harvesting.
It is an object of the present invention to provide a bioanode for use in an enzymatic biofuel cell.
The biological anode provided by the invention comprises carbon cloth, and a three-dimensional nitrogen-doped carbon (3D-NCAIN) layer, a mediator layer (such as a 1, 4-naphthoquinone layer) and a glucose dehydrogenase layer which are sequentially superposed on the carbon cloth.
Furthermore, a Nafion membrane is also arranged on the glucose dehydrogenase layer.
The content of the three-dimensional nitrogen-doped carbon on each square centimeter of the carbon cloth is 0.07-0.35 mg; the content of the 1, 4-naphthoquinone is 0.001-0.004 mmol; the content of the glucose dehydrogenase is 188.3-753.2U.
The invention also provides a preparation method of the biological anode.
The preparation method of the biological anode provided by the invention comprises the following steps:
1) spreading a suspension of three-dimensional nitrogen-doped carbon (3D-NCAIN) on the hydrophilic side of the carbon cloth, and drying to remove the solvent;
2) coating the surface of the carbon cloth treated in the step 1) with a mediator solution, and drying to remove the solvent;
3) applying a Glucose Dehydrogenase (GDH) solution to the surface of the carbon cloth treated in the step 2), and removing the solvent to obtain the carbon cloth.
In the step 1) of the method, the concentration of the three-dimensional nitrogen-doped carbon (3D-NCAIN) suspension is 2-10 mg/mL (specifically, 10mg/mL), and DMF is adopted for preparation.
In step 2) of the above method, the mediator is 1, 4-naphthoquinone; the concentration of the 1, 4-naphthoquinone solution is 50-200 mM (specifically 100mM), and the 1, 4-naphthoquinone solution is prepared from acetonitrile;
in step 3), the GDH solution is prepared in a phosphate buffer solution (e.g., 0.1M pH 7.0PBS) at a concentration of 10-40 mg/mL (e.g., 30 mg/mL).
The drying steps in the step 1) and the step 2) are carried out under the irradiation of infrared light.
The method further comprises the following steps: the glucose dehydrogenase layer was coated with Nafion solution.
It is a further object of the present invention to provide a biocathode for use in enzymatic biofuel cells.
The biological cathode provided by the invention comprises carbon cloth, and a three-dimensional nitrogen-doped carbon (3D-NCAIN) layer and a bilirubin oxidase layer which are sequentially superposed on the carbon cloth.
Furthermore, a Nafion membrane is also arranged on the bilirubin oxidase layer.
The content of the three-dimensional nitrogen-doped carbon on the carbon cloth per square centimeter is 0.2-1.0 mg; the content of the bilirubin oxidase is 44.4-177.6U.
The invention also provides a preparation method of the biological cathode.
The preparation method of the biocathode provided by the invention comprises the following steps:
a) dripping a suspension of three-dimensional nitrogen-doped carbon (3D-NCAIN) on the hydrophilic side of the carbon cloth, and drying to remove the solvent;
b) applying a Bilirubin Oxidase (BOD) solution to the surface of the carbon cloth treated in the step 1), and removing the solvent to obtain the bilirubin oxidase-containing carbon cloth.
In the step a), the concentration of the three-dimensional nitrogen-doped carbon (3D-NCAIN) suspension is 2-10 mg/mL (specifically, 10mg/mL), and the suspension is prepared by DMF.
In the step a), the drying step is performed under irradiation of infrared light.
In the step b), the concentration of the Bilirubin Oxidase (BOD) solution is 10-40 mg/mL (specifically 30mg/mL), and a phosphate buffer solution is adopted for preparation (for example, 0.1M pH 7.0 PBS).
The method further comprises the following steps: a Nafion solution was coated on the bilirubin oxidase layer.
The Carbon Cloth (CC) woven by carbon superfine fibers is used as a current collector for preparing a bioelectrode, and has the characteristics of stable mechanical property, good conductivity and low price. The carbon cloth may be specifically a carbon cloth of a cargo number W1S 1009.
The three-dimensional nitrogen-doped carbon (3D-NCAIN) is prepared by the following method:
thoroughly cleaning a Bacterial Cellulose (BC) film with deionized water, and performing freeze drying treatment to obtain carbon aerogel; then the carbon aerogel is in flowing N 2 And carrying out pyrolysis in the atmosphere to form a black product, and grinding the black product into powder to obtain the three-dimensional nitrogen-doped carbon (3D-NCAIN).
In the method, the freeze drying condition can be-48 ℃ freeze drying for 48 h.
In the above method, the pyrolysis conditions may be: the pyrolysis is carried out to 800 ℃ for 1 hour, and then the pyrolysis is carried out to 1400 ℃ for 2 hours, and the heating rate can be 5 ℃/min.
The invention also protects an enzyme biofuel cell for generating electricity by utilizing the living plants.
The enzyme biofuel cell for generating electricity by using living plants comprises the biological anode, the biological cathode and electrolyte agarose hydrogel.
Wherein the agarose hydrogel is prepared from a 1% agarose solution, and the 1% agarose solution is formulated with 0.1M pH 7.0 PBS.
The enzyme biofuel cell for generating electricity by using living plants also comprises living plants, such as fruits (pears and apples), cactus, aloe and the like.
The invention also provides an enzyme biofuel cell device for generating electricity by using the living plants.
The device comprises an eppendorf pointed-bottom plastic pipe, the biological anode and the biological cathode;
the bottom of the tip of the eppendorf sharp-bottomed plastic tube is cut into a sharp shape, and a hole is drilled in the side wall of the tip; the tip of the eppendorf plastic pointed bottom tube is filled with agarose hydrogel; the bioanode passes through the hole and is inserted into the agarose hydrogel near the hole; the modified surface of the biocathode is placed on agarose hydrogel, and the other side of the biocathode is in direct contact with the air.
When the living plant is used for generating power, the tip of the plastic tube is inserted into the living plant, and the insertion depth can be 1 cm.
When the plastic tip is inserted into a plant, glucose fuel from the biological fluid in a living plant is oxidized at the 3D-NCAIN-based bioanode, while oxygen from the surrounding environment is reduced at the 3D-NCAIN-based biocathode.
The invention also provides a plant activated Enzyme Biofuel (EBFC) stack.
The plant activated Enzyme Biofuel (EBFC) stack provided by the invention comprises a plurality of enzyme biofuel cell devices for generating electricity by living plants; each enzyme biofuel cell device for living plant power generation is inserted into a single plant or an independent split part cut by the plant, and the enzyme biofuel cell devices for living plant power generation are connected in series and/or in parallel.
The invention provides a novel and effective strategy, which can realize reasonable configuration of the battery, thereby exerting the effect of each configuration to the maximum extent and supplying power to different devices according to requirements. When EBFCs are connected in series, a high OCV can be obtained. Thus, the series configuration has great potential to power intermittently operated devices with high drive voltages, such as disposable test devices, calculators, and blood glucose meters. When EBFCs are connected in parallel, a large current and excellent continuous discharge time can be obtained, but the output voltage is not particularly advantageous. The parallel connection may potentially be used to power a continuously operating device that requires a high current but a low operating voltage, such as a watch. By combining the advantages of series and parallel connections, a novel series/parallel connection configuration is proposed to simultaneously increase output current, continuous discharge time and voltage. Such a configuration is expected to power continuously operating devices with high voltage and high power electronics (e.g., wireless sensor systems).
Drawings
FIG. 1 is (a) a schematic representation of the dominance of a living plant; (b) an EBFC schematic diagram and a working mechanism based on 3D-NCAIN; (c) schematic representation of EBFC structure using biochemical energy of living plants; (d) a schematic diagram of the natural inspiration of on-demand power supply.
FIG. 2 is (a) an SEM image of 3D-NCAIN; (b) n of 3D-NCAIN 2 Adsorption-desorption isotherms; (c) XPS spectra of 3D-NCAIN; (d) raman spectrum of 3D-NCAIN; (e) CVs of 3D-NCAIN based bioanode in 0.1M PBS pH 7.0, with and without glucose in the range of 0-100 mM; (f) adding other species to the voltammetric response of the glucose-containing solution in the 3D-NCAIN-based bioanode; (g) 3D-NCAIN-based biocathodes (immersion and diffusion) O 2 Reduced CVs. And in N 2 Control experiments were performed in saturated solution. (h) CV response to 70mM glucose in CC-based bioanode. (i) In N 2 Reducing O with CC-based biocathode in air atmosphere 2 CV of (1). Scanning rates in graphs (e) and (g-i): 5 mV/s. (j) Polarization curves and power output curves for EBFC based on 3D-NCAIN and CC.
FIG. 3 is a graph showing the pore size distribution of the 3D-NCAIN adsorption branch obtained by the DFT method.
FIG. 4 shows HRTEM image (a) and SAED image (b) of 3D-NCAIN.
FIG. 5 is a high resolution XPS spectrum of N1s from 3D-NCAIN.
FIG. 6 shows the IR spectrum of 3D-NCAIN.
FIG. 7 shows (a) GCE and 3D-NCAIN/GCE at 5mM K with 0.1M KCl 3 [Fe(CN) 6 ]CVs profile in solution. Scanning speed: 10 mV/s. (b) GCE and 3D-NCAIN/GCE in 5mM Fe (CN) with 0.1M KCl 6 3-/4- Nyquist diagram in (1).
FIG. 8 is a graph of electrocatalytic current at 0V versus glucose concentration.
FIG. 9 shows CVs of 3D-NCAIN-based bioanode in 70mM glucose without NQ mediator. Scanning speed: 5 mV/s. Electrolyte: 0.1M Ph 7.0 PBS.
FIG. 10 is CVs of 3D-NCAIN based bioanode without GDH enzyme in 70mM glucose. Scanning speed: 5 mV/s. Electrolyte: 0.1M pH 7.0 PBS.
FIG. 11 is CVs in 70mM glucose based on 3D-NCAIN bioanode under 0.1M pH 7.0PBS saturated with nitrogen and air. Scanning rate: 5 mV/s.
Fig. 12 is a polarization curve and a power output curve of the EBFC. Electrolyte: 1% agarose hydrogel, prepared from 0.1M pH 7.0PBS and 70mM glucose.
FIG. 13 shows (a) CVs of 3D-NCAIN-based biocathodes with AA (increasing AA concentration in the direction of the arrow) and without AA. Scanning speed: 5 mV/s. Electrolyte solution: air saturated 0.1M pH 7.0 PBS. (b) Catalytic current of 3D-NCAIN based biocathodes at different AA concentrations.
Fig. 14 is a photograph of an EBFC apparatus designed in (a) length, (b) width, and (c) aperture state.
FIG. 15 shows CVs from 3D-NCAIN-based bioanode insertions into pear (a), apple (b), cactus (c), and aloe (D). Scanning rate: 5 mV/s.
Fig. 16 is a polarization curve and power output curve for EBFC with power harvesting for apple, pear, cactus and aloe.
Fig. 17 is a polarization curve and power output curve of EBFC for power harvesting of apple (a), pear (b)), cactus (c) and aloe vera (d).
FIG. 18 is a graph of the relationship between glucose concentration and maximum cell power in different organisms.
FIG. 19 is a polarization curve and power output curve for a series configuration formed by inserting two pairs of biocatalytic electrodes into a single fruit.
Fig. 20 is (a) a plot of relative polarization and power density for different cells connected in series. (b) Relative polarization and power density curves for different cells connected in parallel. (c) Polarization curves and power output curves of four EBFCs connected in two series-two parallel. (d) The relation between the number of the battery cells and the performance when the battery cells are connected in series or in parallel.
Fig. 21 is a relationship between the number of batteries arranged in series and the internal resistance.
Fig. 22 shows the relationship between the number of cells and the internal resistance in the parallel structure.
Fig. 23 is a polarization curve and a power output curve of n-EBFCs in series (a), parallel (b), and a-series/b-parallel (c). Polarization curves and power density curves for 8-EBFC series (e), 8-EBFC parallel (f), and 4-EBFC series/2-EBFC parallel (g); .
FIG. 24 shows (a) the operational stability of 5mM glucose on 3D-NCAIN-based bioanode. Applying a potential: 0V. (b) Operational stability of 3D-NCAIN based biocathodes. Applying a potential: 0V. Electrolyte solution: air saturated 0.1M pH 7.0 PBS.
FIG. 25 shows (a) the storage stability of 5mM glucose on 3D-NCAIN-based bioanode. Applying a potential: 0V. (b) Storage stability of 3D-NCAIN based biocathodes. Applying a potential: 0V. Electrolyte: air saturated 0.1M pH 7.0 PBS.
FIG. 26 shows (a) discharge curves for different configurations with constant current 50 μ A to continuous discharge time 11 hours. (b) The discharge curves for the different configurations were run at a constant current of 50 μ A until the cell voltage reached 0.30V. (c) Discharge curve of bicell series/bicell parallel at constant current of 50 μ a. (d) A calculator power wiring scheme consisting of five EBFCs in series. (e) A digital photograph of the design configuration of the computer is activated. (f) Voltage change during test run was recorded.
Fig. 27 is a discharge curve of two battery packs (a), three battery packs (b), and four battery packs (c) at a constant current of 30 μ a.
Figure 28 is a demonstration of the calculator being powered on when the series circuit is open.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Glucose Dehydrogenase (GDH) used in the following examples was purchased from positive-enzymes, catalog No. NATE-0251, and had an enzyme activity of 538U/mg; bilirubin Oxidase (BOD) was purchased from Shanghai-derived leaf Biotechnology Ltd under catalog number S31000 and had an enzyme activity of 37U/mg.
EXAMPLE 1 Synthesis of three-dimensional Nitrogen-doped carbon assembled from interwoven nanofibers (3D-NCAIN)
First, fresh Bacterial Cellulose (BC) film was thoroughly washed with deionized water and cut into rectangular pieces (3X 3 cm) 2 ). The cleaned slices were then turned into carbon aerogels by freeze-drying treatment (-48 ℃, 48 h). Finally, the sample is flowing N 2 Under an atmosphere (heating rate of 5 ℃ C. for min) -1 ) Pyrolyzed to 800 ℃ for 1 hour, then to 1400 ℃ for 2 hours to form a black product. After grinding the material into powder using a mortar, 3D-NCAIN was obtained and stored at room temperature.
Example 2 preparation of enzymatic biofuel cell (EBFC)
Carbon Cloth (CC) woven by carbon superfine fiber is used as a current collector for preparing a bioelectrode, and has the characteristics of steady mechanical property, good conductivity and low price.
To prepare a 3D-NCAIN-based bioanode, 35. mu.L of 3D-NCAIN suspension (10mg/mL, prepared from DMF) was spread on a block of CC (0.5 cm) 2 Item number W1S 1009). After evaporation of the solvent under infrared irradiation, the electrode was further coated with 20 μ L of 1, 4-naphthoquinone (NQ, 0.1M, prepared in acetonitrile). Then 35. mu.L of Glucose Dehydrogenase (GDH) solution (30mg/mL, prepared from 0.1M pH 7.0PBS) was applied to the electrode and the electrode was stored in a refrigerator at 4 ℃ for 3 hours. Finally, the electrode was coated with 10 μ L of 0.5% Nafion solution (diluted with ethanol) and dried at room temperature.
To prepare a 3D-NCAIN-based biocathode, 100. mu.L of 3D-NCAIN suspension (10mg/mL, prepared from DMF) was applied to a piece of CC (1.0 cm) 2 Item number W1S1009) and dried under irradiation of infrared light. Subsequently, 120. mu.L of Bilirubin Oxidase (BOD) solution (30mg/mL, prepared from 0.1M pH 7.0PBS) was applied to the electrode. After drying in a refrigerator at 4 ℃, the electrode was coated with 20 μ L of 0.5% Nafion solution.
For comparison, a CC-based bioelectrode was prepared by using the same procedure as described above, except that the 3D-NCAIN suspension did not diffuse to the electrode surface.
Example 3 enzymatic biofuel cell (EBFC) measurements
A test device for energy harvesting from biological fluids in live fruit was constructed using eppendorf plastic tip chambers filled with 1% agarose, prepared with 0.1M pH 7.0 PBS. The bottom of the plastic tip was cut to a sharp shape and a hole of about 5mm in diameter was drilled in the sidewall. The bioanode was inserted into the hydrogel in the vicinity of the aperture and then the modified side of the biocathode was placed on the agarose hydrogel with the other side in direct contact with air. The device was mounted in fruit at a depth of about 1cm and the open circuit voltage of the fruit activated EBFC was evaluated by connecting the bioanode and biocathode in the CHI 760E electrochemical workstation. After voltage stabilization, the cell was connected to an external resistor of 10 Ω to 100k Ω and polarization and power density output were determined by using two digital multimeters.
1. Characterization of enzymatic biofuel cells (EBFC)
The performance of the bioanode and biocathode was characterized under conditions similar to those of the in situ power generation of the biofluid prior to EBFC implantation. A bioanode was formed by sequential decoration of three-dimensional nitrogen-doped carbon assembled from interwoven nanofibers (3D-NCAIN), Glucose Dehydrogenase (GDH) and 1, 4-Naphthoquinone (NQ) on a carbon cloth electrode (CC), the bioanode catalyst GDH oxidizing glucose through the mediator NQ. On the other hand, bilirubin oxidase ((BOD) is immobilized on 3D-NCAIN to form a biocathode, which directly catalyzes the reduction of oxygen.
The carbon material of 3D-NCAIN was synthesized due to its unique structure inducing excellent electrochemical properties and was selected as a suitable electrode substrate for glucose EBFC. The 3D-NCAIN exhibits a mechanically robust interwoven nanofiber network structure with a high specific surface area (112.33 m) 2 G), broad pore size distribution centered at 2.6, 4.1 and 13.2nm and 0.15cm 3 A large pore volume per gram (FIGS. 2a-b and 3), which may contribute to high quality and compact enzyme loading as well as unobstructed species permeation and transport. These characteristics are advantageous in accelerating electron transfer on the surface of the bioelectrode, thereby improving the power generation capacity of the EBFC. High I in Raman spectra D /I G The value (1.58) indicates that abundant edge-plane defects exist in 3D-NCAIN, which can promote electron transfer (FIG. 2 c). High resolution TEM and selected area electron diffraction patternThe amorphous nature of 3D-NCAIN was achieved (FIG. 4). The presence of N1s in X-ray photoelectron spectroscopy (XPS) spectra (fig. 2D and 5) confirmed successful N doping in 3D-NCAIN, which may provide more reactive sites and thus enhance electrocatalytic activity. Fourier transform infrared (FT-IR) spectroscopy confirmed that the presence of different kinds of oxygen-containing functional groups in 3D-NCAIN can improve the wettability of the carbon surface, thereby facilitating enzyme immobilization and charge transfer (fig. 6). Using K 3 [Fe(CN) 6 ]As a probe, the 3D-NCAIN modified glassy carbon electrode (GCE, D3 mm) had a height of 0.089cm as compared with GCE 2 Larger active area and lower potential separation (65mV) (0.069 cm2 and 80mV) (FIG. 7 a). The lower electron transfer resistance of the 3D-NCAIN modified GCE (113.6 Ω) was further verified compared to GCE (301.8 Ω) (FIG. 7 b). The results not only indicate that 3D-NCAIN has excellent electrochemical reactivity, but also make it very attractive as an electrode substrate for EBFC structures.
By introducing 3D-NCAIN as an electrode substrate into EBFC, the 3D-NCAIN-based bioanode shows excellent and well-defined electrochemical response to glucose oxidation over a wide concentration range, which enables the 3D-NCAIN-based bioanode to make full use of glucose in plants, since glucose levels in plants are typically in the order of tens of millimoles (fig. 2 e). In the absence of glucose, only redox reactions of the NQ mediator at-0.15V were observed. After increasing the glucose concentration, the voltammetric response of the 3D-NCAIN based bioanode increased linearly over the concentration range of 10-80mM (FIG. 8). Comparative experiments further showed that NQ communicated the redox active center of GDH to the electrode to complete the oxidation process (FIGS. 9-11). Furthermore, 3D-NCAIN-based bioanode showed excellent selectivity for potential co-existence interference in real fruit containing organic acids, carbohydrates and amino acids (fig. 2 f). For 3D-NCAIN based biocathodes, direct electrochemistry of BOD is demonstrated by very close potentials between the initial potential (0.54V) and the formal potential reported in the literature for BOD TI sites (fig. 2 g). Meanwhile, the reduction current is in direct proportion to the oxygen content of the electrolyte, and the advantage of effectively supplying oxygen from the ambient air is highlighted. For comparison, the electrochemical performance of the bioelectrode without the introduction of 3D-NCAIN (CC-based bioanode and biocathode) was also evaluated (fig. 2 h-i). The superior performance of the 3D-NCAIN-based electrode in terms of glucose electrooxidation or oxygen electroreduction was more than 5 times higher by current response than the CC-based electrode with the aid of Cyclic Voltammetry (CV), demonstrating the feasibility of 3D-NCAIN as a high-performance electrode substrate for constructing a glucose EBFC with enhanced performance.
O with biocathodes 2 The presence of glucose, compared to electroreduction, makes the starting potential of the glucose-electrooxidation bioanode lower, which allows spontaneous generation of current according to the galvanic principle. The Open Circuit Voltage (OCV) and the maximum power of the EBFC based on 3D-NCAIN are 0.73V and 200.1 μ W (i.e. 400.2 μ W/cm) respectively 2 ) Not only higher than EBFC without 3D-NCAIN (0.65V and 43.8 muW), but also comparable to the reported EBFC (FIG. 2j), indicating the important role of 3D-NCAIN in promoting the generation of electricity from bioenergy. The substitution of solid agarose prepared with 0.1M pH 7.0PBS containing 70mM glucose as an electrolyte for the above solution had negligible effect on cell performance, indicating that agarose does not bring about the resistive effect between the bioanode and biocathode (FIG. 12), making it very promising for power generation using natural plants.
2. Meter evidence for obtaining electric energy from single plant by enzyme biological fuel cell
Power generation from metabolically produced carbohydrates is a potential green energy technology, and biological fluids from living plants can be used directly as biofuels without purification. Unfortunately, biological fluids often contain certain amounts of biocathode enzyme inhibitors, such as Ascorbic Acid (AA), resulting in a substantial decrease in performance (fig. 13). Therefore, an EBFC apparatus for plant power generation was designed, which employs eppendorf plastic tips filled with agarose hydrogel prepared with 0.1M pH 7.0PBS, effectively reducing interference and facilitating proton flow from the bioanode to the biocathode. A hole of about 5mm in diameter was drilled in the side wall of the eppendorf plastic tip to promote efficient supply of biofuel (fig. 14). When the plastic tip is inserted into a plant, glucose fuel from the biological fluid in a living plant is oxidized at the 3D-NCAIN-based bioanode, while oxygen from the surrounding environment is reduced at the 3D-NCAIN-based biocathode.
The power generation of the designed EBFC device is demonstrated in four typical plants (pear, apple, cactus and aloe). The electrochemical performance of the bioanode in four plants was first evaluated using an externally inserted counter and reference electrode (fig. 15). To verify that biological fluids in plants do not penetrate into them, the performance of the bioanode in agarose remote from the pear juice was also evaluated. After 24 hours of insertion of the device into the pear, no catalytic current was observed, demonstrating the feasibility of designing the device. The glucose content of these plants can be calculated using the linear relationship shown in figure 8 and the results are summarized in figure 16. When EBFCs were inserted into plants, their OCV's were nearly identical, but their maximum power in pear, apple, cactus and aloe was 123 μ W and 156.2 μ W, 64.52 μ W and 32.02 μ W, respectively (fig. 3). The difference in battery energy is mainly due to the difference in glucose levels in plants. It is noteworthy that plant-activated EBFCs produce electrical outputs (OCV, maximum current or maximum power) that are comparable to, or even superior to, other published living organism-activated EBFCs. For example, in 2020, Miyake's group reported that insertion of designed EBFCs into grapes, apples and kiwifruits achieved powers of 55 μ W, 33 μ W and 44 μ W, respectively [6 ]. The excellent results are attributed to technical and scientific improvements: (1) 3D-NCAIN with abundant active sites and unique structure is selected as a suitable electrode substrate to improve the electron transfer rate. (2) Agarose hydrogel prepared with 0.1M pH 7.0PBS can effectively promote ionic conduction and pH stability. (3) A gas diffusion type biocathode for efficiently supplying oxygen from ambient air and avoiding inhibition to ensure efficient electroreduction of oxygen.
It was surprisingly found that the maximum power of organism activated EBFC increased linearly with the glucose concentration in the living organism (fig. 18). Since glucose in the biological fluid reacts with the anode enzyme in the EBFC to generate electric energy, the energy extracted from the biological fluid depends on the glucose concentration. Therefore, the growth state of the plant can also be judged by calculating the glucose concentration from the power generation amount.
EBFC Stack evaluation
Although the introduction of 3D-NCAIN has improved the voltage and current output of a single cell, EBFC still produces relatively low power, insufficient to power some microelectronic devices (light emitting diodes, calculators, etc.). Inspired by powered fish, a plant activated EBFC stack was proposed that included various configurations, such as series, parallel, and both series and parallel, to increase the power output of cells implanted in living plants. As proof of concept, we selected a pear for experiment and then split it into two, three or four parts to form seven different configurations of glucose/O 2 An EBFC stack.
In the series connection, we initially tried to assemble two pairs of bioanode-biocathode stacks into a single fruit with a series connection (fig. 19). However, the EBFC configuration showed little change in voltage, 0.73V, much less than the expected quadruple voltage. This negative result may be explained by the conductivity of biological tissue forming a low impedance path between the biocatalytic electrodes, preventing the intended series operation of four EBFCs. Unsuccessful experiments indicate that EBFCs cannot be connected in series when operated in the same organism. Here we describe a strategy of inserting biocatalytic electrodes into different dividing parts of a fruit and connecting cells in series, which can be done with only one fruit. Two, three or four pairs of biocatalytic electrodes are inserted into two, three or four sections of a single pear, respectively, including three different series configurations. As shown in fig. 20a, the shape of the polarization curves and the power output curves of these series arrangements are identical. As expected, two connected EBFCs achieved a stable OCV of 1.42V, while three and four connected EBFCs increased the OCV to 2.13V and 2.85V, respectively (table 1). Likewise, the maximum power is significantly increased by a factor of 1.85, 2.84 and 3.77 over connecting two, three and four cells, respectively. As observed in fig. 21, the internal resistance increases linearly with the number of series-connected cells.
In the parallel configuration, OCV was the same as expected for the different EBFCs connected in parallel at 0.72V, while slight voltage fluctuations were attributed to voltage differences in the individual cells (fig. 20b and table 1). On the other hand, the maximum current linearly increases with the number of connected EBFCs. Two connected EBFCs obtained a high current of 1.38mA, while three and four connected EBFCs increased the current to 2.07 and 2.75mA, respectively. Similarly, the power output is also increased accordingly, with two cells having a maximum power of 0.26mW, three of 0.38mW, four of 0.52mW, which are respectively 1.97, 2.92 and 3.94 times the maximum power provided by a single EBFC. Series connections produce higher output voltages than single cells or parallel connections and increase linearly with the number of cells connected. Furthermore, the parallel connection produces higher output current and power than a single cell or series connection, mainly due to the proportional decrease in internal resistance resulting from the increased number of parallel connections (fig. 22).
Finally, a third series/parallel connection (2-S/2-P) was proposed and evaluated (FIG. 20 d). Here, the number of batteries is expressed as (the number of batteries connected in series) × (the number of batteries connected in parallel). Interestingly, the OCV (1.42V) was very close to 1.43V, with only two EBFCs in series, and a maximum current of 1.37mA was 1.95 times that of the two cells in series. Although this type of configuration provides no increase in current compared to only two parallel EBFCs, the OCV is 1.97 times higher than it. This type produces maximum powers of 0.50mW 2.08 and 1.92 times that of two series and parallel cells, respectively. The internal resistance of such a connection should theoretically be equal to 2 x r/2 (i.e. 997.1 omega, r: cell internal resistance) according to the previous law of series and parallel resistances, which is almost identical to the experiment, resulting in a value calculated with the linear part of the polarization curve in fig. 20d (-1008.2 omega). The current and the voltage which are increased simultaneously in series-parallel connection are mainly due to the fact that the advantages of series-parallel connection are inherited.
Table 1 summary of performance obtained for different stack configurations. Each data represents the average of three independent measurements
4. Characterization of Power tunable EBFC
In order to meet the power supply requirements of different electrical devices, it is necessary to develop a power-adjustable EBFC. Here, the evaluation and summarization of different series-parallel electrical outputs from n (defined as natural numbers) fruit segments can provide reasonable guidance for the desired configuration of different electronic devices. The electrochemical parameters of these configurations can be simulated and reproduced by an equivalent circuit model, each cell represented as a series connection of an electromotive force and a virtual internal resistance. Fig. 23a-c show the theoretical performance of the equivalent circuit model and different configurations. According to the rules summarized in the series, it is predicted that the current, voltage and internal resistance of the n series arrangement are about 0.69mA, 0.72n V and-997.1 n Ω, respectively, and the maximum power can be calculated to be 1000 × (nE) based on equation S2-4 2 /(4nr) mW. By derivation of the formula, it can be concluded that the power of the battery reaches the maximum value when the external resistance and the internal resistance are equal, which is consistent with literature reports. Similarly, the current, voltage, and internal resistance for the n-parallel configuration can also be predicted to be about 0.69 nmA, 0.72V, and 997.1/n Ω, respectively, and the maximum power can be calculated according to equation S5-7. For the third a-S/b-P connection, a current of 0.69 nmA, a voltage of 0.72a V and an internal resistance of 997.1a/b Ω can be predicted, and the maximum power can be calculated according to the formula S8-10. As shown in table 1, the three types of connections can increase power by increasing voltage or current or increasing EBFC simultaneously.
To verify the feasibility of on-demand power regulation, a milliwatt power target was proposed and demonstrated based on the above results. Since the difference per cell is not very large, the internal resistances of the different configurations can be calculated from the average internal resistance (r) of the single pear activating EBFC. Using the summarized theoretical performance derived from different configurations, it is reasonable to estimate that at least 8 cells can be connected in series, parallel or both (fig. 23d) to achieve this goal. The polarization and power density curves for the three connection configurations are shown in fig. 23 e-g. As expected, each connection completes a milliwatt of power. The voltage of the series 8-EBFC (5.69V) was significantly increased by a factor of 7.80 compared to a single cell (0.73V), correspondingly yielding a total power output of 1.02 mW. The maximum current (5.51mA) in parallel is increased by 7.9 times compared with a single battery, so that the power output is 1.15 mW. Series/parallel increases both the voltage and current of the cell, resulting in a significant increase in power output (1.05 mW). Based on experimental and simulation results of different configurations, the EBFC stack can be reasonably configured, power supply of different devices as required is realized, and the limitation of the EBFC stack on the aspect of activating electronic devices is expected to be reduced.
EBFC Stack on demand application
The stability of the EBFC stack is a very important factor in addition to power output for on-demand power supply. The superior handling and storage stability of 3D-NCAIN-based bioanode and biocathode make it promising long-term continuous harvesting of bioenergy in living plants (fig. 24-25). On this basis, the operational stability of the series connection was investigated by performing a constant current discharge at 50 μ a for a long time (fig. 26 a). It is clear that EBFC shows a considerable voltage drop during the first 3 minutes, followed by a slow decline with discharge time. The maximum residual voltage (2.42V) was obtained with four cells in series, three cells (1.68V) next, and two cells (1.17V) last. The results show that after the same discharge time, the working voltage is proportional to the number of the batteries connected in series, and further prove that the output voltage of the batteries can be improved by connecting in series. For the parallel connection, the continuous discharge time before the cell voltage dropped to 0.3V was analyzed to evaluate the stability at a constant current of 50 μ a (fig. 26 b). Obviously, the discharge time of four parallel batteries can last for 62.79h, which is 1.37 times longer and 2.14 times longer than three batteries and two batteries respectively. It can be concluded that the duration of the continuous discharge is related to the battery current, which means that more batteries in parallel can theoretically be used for a longer time. For comparison, the same test was performed on the series circuit. When 2, 3 and 4 batteries are connected in series, respectively, the discharge time is reduced to 17.90, 26.1 and 32.05h, respectively, less than half of that when the same number of batteries are connected in parallel (fig. 27). Not to be neglected, all curves of the series configuration show a sharp drop after a period of time. This phenomenon may be due to local fuel shortages, or impedance differences or enzyme deactivation leading to power losses in some individual cells, resulting in an inherent catalytic efficiency that does not meet the power output [5 ]. In addition, the parallel series can achieve 35.16h discharge time, much higher than two batteries in series (fig. 26c), indicating the advantages of series/parallel in current and voltage.
The goal of this work was to propose a novel and effective strategy that would allow for the proper configuration of the batteries, maximizing the effectiveness of each configuration, and powering different devices as needed. As described above, when EBFCs are connected in series, a high OCV can be obtained, but a relatively low current and a non-competitive continuous discharge time cannot be ignored. Thus, the series configuration has great potential to power intermittently operated devices with high drive voltages, such as disposable test devices, calculators, and blood glucose meters. In practical application, if the voltage drops due to local glucose consumption on the surface of the electrode, the device can not be driven, only a certain time is needed for waiting, and when the glucose concentration is recovered to the original level, the device can be activated again. When EBFCs are connected in parallel, a large current and excellent continuous discharge time can be obtained, but the output voltage is not particularly advantageous. The parallel connection may potentially be used to power a continuously operating device that requires a high current but a low operating voltage, such as a watch. By combining the advantages of series and parallel connections, a novel series/parallel connection configuration is proposed to simultaneously increase output current, continuous discharge time and voltage. Such a configuration is expected to power continuously operating devices with high voltage and high power electronics (e.g., wireless sensor systems).
To demonstrate the utility of on-demand power, we chose a calculator as a simple example model electronic device to drive. The calculator is a common and frequently-used device, has short running time each time and belongs to an intermittent running device. In preliminary experiments, we found that the minimum drive voltage required by the calculator when powered by a variable power supply was 3V. Since this voltage cannot be obtained from a single EBFC, five pairs of bioelectrodes were assembled to form five series cells, thereby increasing the output voltage to the power calculator (fig. 26 d). The output of such a configuration is applied to the calculator and the model electronics successfully activated (fig. 26 e). In contrast, when the configuration is not applied to the calculator, the calculator cannot be driven (fig. 28). Under the same experimental conditions, the calculator was further connected to a workstation (not shown) to record the voltage changes (fig. 26 f). As soon as the calculator was turned on, the voltage dropped almost linearly from 3.51V to 3.09V in the first 20 seconds and then stabilized. To simulate the actual application, the calculator was set to operate continuously for 30 minutes. When the calculator is turned off, the battery voltage may return to its original OCV after 15 minutes, and the battery configuration may then be ready again for further testing. After a total of 5 tests using the stack, the measurable performance showed negligible loss. The power and life of the design configuration meet the specifications of the calculator and represent the first practical application if EBFC is activated. The first demonstration of a physiologically generated power activated calculator shows that it shows a great potential to activate various electronic devices with only one fruit to achieve on-demand use.
In conclusion, we propose a power-adjustable plant-activated EBFC through the strategy of EBFC stack, thereby realizing on-demand power supply and successfully proving its feasibility. Electrochemical performance of various configurations (e.g., series, parallel, and series/parallel) was studied in detail in terms of voltage, current, power, and stability. The rules of voltage, current and power for different configurations are summarized to obtain the theoretical performance of the connected n-EBFC. Thus, the output performance can be easily adjusted as needed, without complicated operating procedures and easily extensible processes, providing a sustainable and clean power source. Taking the application of milliwatt power as an example, theoretically at least eight battery connections are required. Not surprisingly, the configuration of the 8-EBFC stack actually achieves mW level performance by increasing the current, voltage, or both current and voltage corresponding to the series, parallel, or series/parallel connection. Therefore, the proposed EBFC stack may help to take important achievements directly from the aspect of power generation from living organisms and reduce the limitation of activating electronic devices in different application scenarios. The work that follows will focus on developing more enzymatic systems that can use other biofuels than glucose in plants, such as cellulose, starch, etc. present in plants, to complete the range of application of our system and achieve true, geographically unconstrained, on-demand power supply.
Claims (10)
1. An enzyme biofuel cell for generating electricity by using living plants comprises a biological anode, a biological cathode and electrolyte agarose hydrogel;
the biological anode comprises carbon cloth, and a three-dimensional nitrogen-doped carbon layer, a dielectric layer and a glucose dehydrogenase layer which are sequentially superposed on the carbon cloth;
the biological cathode comprises a carbon cloth, and a three-dimensional nitrogen-doped carbon layer and a bilirubin oxidase layer which are sequentially superposed on the carbon cloth;
the agarose hydrogel was prepared from a 1% agarose solution.
2. The enzyme biofuel cell of claim 1 wherein: the enzyme biofuel cell takes biofluid glucose in living plants as biofuel;
the mediator is 1, 4-naphthoquinone;
in the biological anode, the content of the three-dimensional nitrogen-doped carbon is 0.07-0.35 mg per square centimeter of the carbon cloth; the content of the 1, 4-naphthoquinone is 0.001-0.004 mmol; the content of the glucose dehydrogenase is 188.3-753.2U;
in the biological cathode, the content of the three-dimensional nitrogen-doped carbon is 0.2-1.0 mg per square centimeter of the carbon cloth; the content of the bilirubin oxidase is 44.4-177.6U.
3. An enzyme biofuel cell device for the power generation of living plants, comprising eppendorf spiked-bottom plastic tube, the bioanode, the biocathode and electrolyte agarose hydrogel;
the bottom of the tip of the eppendorf plastic tip bottom tube is cut into a sharp shape, and a hole is drilled in the side wall of the tip; the tip of the eppendorf plastic pointed bottom tube is filled with agarose hydrogel; the bioanode passes through the aperture and inserts into the agarose hydrogel adjacent to the aperture; the modified side of the biological cathode is placed on agarose hydrogel, and the other side of the biological cathode is in direct contact with air.
4. The enzyme biofuel cell device of claim 3 wherein: when the living plant is used for generating power, the tip of the plastic tube is inserted into the living plant to the depth of 1 cm.
5. A plant activated enzyme biofuel stack comprising a plurality of enzyme biofuel cell devices of claim 3 or 4 for the generation of electricity from living plants; the enzyme biofuel cell devices for the power generation of the living plants are connected in series and/or in parallel.
6. The plant-activated enzyme biofuel stack of claim 5 wherein: each of the enzyme biofuel cell devices for living plant power generation is inserted into a single plant or a separate split part cut from a plant, respectively.
7. A biological anode for an enzymatic biological fuel cell comprises a carbon cloth, and a three-dimensional nitrogen-doped carbon layer, a dielectric layer and a glucose dehydrogenase layer which are sequentially stacked on the carbon cloth.
8. The bioanode of claim 7, wherein: a Nafion membrane is also arranged on the glucose dehydrogenase layer;
the mediator is 1, 4-naphthoquinone;
the content of the three-dimensional nitrogen-doped carbon on the carbon cloth per square centimeter is 0.07-0.35 mg; the content of the 1, 4-naphthoquinone is 0.001-0.004 mmol; the content of the glucose dehydrogenase is 188.3-753.2U.
9. A method of preparing a bioanode as claimed in claim 7 or 8, comprising the steps of:
1) dripping the suspension of the three-dimensional nitrogen-doped carbon on the hydrophilic side of the carbon cloth, and drying to remove the solvent;
2) coating the surface of the carbon cloth treated in the step 1) with a mediator solution, and drying to remove the solvent;
3) applying a glucose dehydrogenase solution to the surface of the carbon cloth treated in the step 2), and removing the solvent to obtain the carbon cloth;
preferably, in the step 1), the concentration of the three-dimensional nitrogen-doped carbon (3D-NCAIN) suspension is 2-10 mg/mL, and the suspension is prepared by DMF;
in the step 2), the mediator is 1, 4-naphthoquinone; the concentration of the 1, 4-naphthoquinone solution is 50-200 mM and prepared by adopting acetonitrile;
in the step 3), the concentration of the glucose dehydrogenase solution is 10-40 mg/mL, and a phosphate buffer solution is adopted for preparation.
10. The enzyme biofuel cell of claim 1 or 2, the device of claim 3 or 4, the plant-activated enzyme biofuel stack of claim 5 or 6, the bioanode of claim 7 or 8, the method of preparing of claim 9, characterized in that:
the three-dimensional nitrogen-doped carbon is prepared by the following method:
thoroughly cleaning the bacterial cellulose film with deionized water, and performing freeze drying treatment to obtain carbon aerogel; then the carbon aerogel is in flowing N 2 Pyrolyzing in the atmosphere to form a black product, and grinding the black product into powder to obtain three-dimensional nitrogen-doped carbon;
preferably, the freeze drying condition is-48 ℃ freeze drying for 48 h;
the pyrolysis conditions are as follows: pyrolyzing to 800 deg.C for 1 hr, and then pyrolyzing to 1400 deg.C for 2 hr at a heating rate of 5 deg.C/min.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158458A (en) * | 2007-12-06 | 2009-07-16 | Sony Corp | Fuel cell, method of manufacturing fuel cell, electronic apparatus, enzyme immobilization electrode, biosensor, bioreactor, energy conversion element, and enzyme reaction utilization device |
| CN101573816A (en) * | 2007-01-05 | 2009-11-04 | 埃克民公司 | Bioanode and biocathode stack assemblies |
| CN102089917A (en) * | 2008-07-14 | 2011-06-08 | 索尼公司 | Fuel reformer and power generation apparatus using the fuel reformer |
| CN102171880A (en) * | 2008-10-06 | 2011-08-31 | 索尼公司 | Fuel cell and enzyme electrode |
| CN102757013A (en) * | 2012-06-11 | 2012-10-31 | 华中科技大学 | Preparation method for three-dimensional carbon micro-nano electrode array structure integrating carbon nano-drape |
| CN103339779A (en) * | 2011-01-31 | 2013-10-02 | 索尼公司 | Fuel cell, method for manufacturing fuel cell, electronic apparatus, nicotinamide adenine dinucleotide-immobilized electrode, nicotinamide adenine dinucleotide-immobilized carrier, device using enzyme reaction, protein-immobilized electrode, and prot |
| US9356297B1 (en) * | 2012-04-27 | 2016-05-31 | Stc.Unm | Facile fabrication of scalable, hierarchically structured polymer-carbon architectures for bioelectrodes |
| CN105717177A (en) * | 2016-02-04 | 2016-06-29 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Electrode and preparation method thereof, biosensor and enzyme biofuel cell |
| CN111146451A (en) * | 2019-12-27 | 2020-05-12 | 扬州大学 | Lotus root starch carbon sphere biofuel cell and preparation method thereof |
| CN111326743A (en) * | 2019-12-09 | 2020-06-23 | 中国人民解放军军事科学院军事医学研究院 | Application of porous carbon derived from bamboo as electrode material for glucose biosensing and glucose biofuel cell |
| CN114023981A (en) * | 2021-07-26 | 2022-02-08 | 中国人民解放军军事科学院军事医学研究院 | Application of composite catalytic cascade reaction in glucose fuel cell |
-
2022
- 2022-05-25 CN CN202210573790.7A patent/CN114927735B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101573816A (en) * | 2007-01-05 | 2009-11-04 | 埃克民公司 | Bioanode and biocathode stack assemblies |
| JP2009158458A (en) * | 2007-12-06 | 2009-07-16 | Sony Corp | Fuel cell, method of manufacturing fuel cell, electronic apparatus, enzyme immobilization electrode, biosensor, bioreactor, energy conversion element, and enzyme reaction utilization device |
| CN102089917A (en) * | 2008-07-14 | 2011-06-08 | 索尼公司 | Fuel reformer and power generation apparatus using the fuel reformer |
| CN102171880A (en) * | 2008-10-06 | 2011-08-31 | 索尼公司 | Fuel cell and enzyme electrode |
| CN103339779A (en) * | 2011-01-31 | 2013-10-02 | 索尼公司 | Fuel cell, method for manufacturing fuel cell, electronic apparatus, nicotinamide adenine dinucleotide-immobilized electrode, nicotinamide adenine dinucleotide-immobilized carrier, device using enzyme reaction, protein-immobilized electrode, and prot |
| US9356297B1 (en) * | 2012-04-27 | 2016-05-31 | Stc.Unm | Facile fabrication of scalable, hierarchically structured polymer-carbon architectures for bioelectrodes |
| CN102757013A (en) * | 2012-06-11 | 2012-10-31 | 华中科技大学 | Preparation method for three-dimensional carbon micro-nano electrode array structure integrating carbon nano-drape |
| CN105717177A (en) * | 2016-02-04 | 2016-06-29 | 中国人民解放军军事医学科学院放射与辐射医学研究所 | Electrode and preparation method thereof, biosensor and enzyme biofuel cell |
| CN111326743A (en) * | 2019-12-09 | 2020-06-23 | 中国人民解放军军事科学院军事医学研究院 | Application of porous carbon derived from bamboo as electrode material for glucose biosensing and glucose biofuel cell |
| CN111146451A (en) * | 2019-12-27 | 2020-05-12 | 扬州大学 | Lotus root starch carbon sphere biofuel cell and preparation method thereof |
| CN114023981A (en) * | 2021-07-26 | 2022-02-08 | 中国人民解放军军事科学院军事医学研究院 | Application of composite catalytic cascade reaction in glucose fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| CUIXING XU ET.AL: "Banana peel derived nitrogen-doped porous carbon with enhanced electrocatalytic activity for complete oxidation of methanol under room temperature", 《SENSORS AND ACTUATORS: B. CHEMICAL》 * |
| 库里松・哈衣尔别克;曾涵;: "介孔碳掺杂氮材料-壳聚糖固定漆酶电极的直接电化学行为及化学传感性能", 应用化学, no. 10 * |
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