CN114023981B - Application of composite catalytic cascade reaction in glucose fuel cell - Google Patents
Application of composite catalytic cascade reaction in glucose fuel cell Download PDFInfo
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- CN114023981B CN114023981B CN202110842770.0A CN202110842770A CN114023981B CN 114023981 B CN114023981 B CN 114023981B CN 202110842770 A CN202110842770 A CN 202110842770A CN 114023981 B CN114023981 B CN 114023981B
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 158
- 239000008103 glucose Substances 0.000 title claims abstract description 158
- 239000000446 fuel Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims description 7
- 230000003197 catalytic effect Effects 0.000 title abstract description 35
- 238000010523 cascade reaction Methods 0.000 title description 2
- 108010015776 Glucose oxidase Proteins 0.000 claims abstract description 74
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- 229940116332 glucose oxidase Drugs 0.000 claims abstract description 73
- 235000019420 glucose oxidase Nutrition 0.000 claims abstract description 73
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 62
- 230000003647 oxidation Effects 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 108010050375 Glucose 1-Dehydrogenase Proteins 0.000 claims abstract description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000002551 biofuel Substances 0.000 claims description 8
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- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
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- IAJILQKETJEXLJ-QTBDOELSSA-N aldehydo-D-glucuronic acid Chemical compound O=C[C@H](O)[C@@H](O)[C@H](O)[C@H](O)C(O)=O IAJILQKETJEXLJ-QTBDOELSSA-N 0.000 abstract description 9
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- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 description 12
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 4
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- YPZRHBJKEMOYQH-UYBVJOGSSA-N FADH2 Chemical compound C1=NC2=C(N)N=CN=C2N1[C@@H]([C@H](O)[C@@H]1O)O[C@@H]1COP(O)(=O)OP(O)(=O)OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C(NC(=O)NC2=O)=C2NC2=C1C=C(C)C(C)=C2 YPZRHBJKEMOYQH-UYBVJOGSSA-N 0.000 description 3
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
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- QQODLKZGRKWIFG-UHFFFAOYSA-N cyfluthrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=C(F)C(OC=2C=CC=CC=2)=C1 QQODLKZGRKWIFG-UHFFFAOYSA-N 0.000 description 1
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- 150000002303 glucose derivatives Chemical class 0.000 description 1
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- 235000014655 lactic acid Nutrition 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
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- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 relates to the technical field of fuel cells, in particular to an anode catalyst for a fuel cell and a glucose fuel cell containing the anode catalyst. The present invention provides an anode catalyst for a fuel cell and a glucose fuel cell capable of mediating electron transfer between a glucose oxidase/glucose dehydrogenase redox centre and an electrode surface using 2, 6-tetramethyl-1-piperidyl N-oxy (TEMPO). Meanwhile, TEMPO can oxidize glucose into glucuronic acid under mild conditions, a compound enzyme-organic cascade (HEOC) system of glucose 4 e-oxidation is realized, the catalytic efficiency of glucose oxidation is improved, and TEMPO becomes a promising alternative catalyst for glucose oxidation in application of bioelectronic devices.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to an anode catalyst for a fuel cell and a glucose fuel cell containing the anode catalyst.
Background
Glucose has the advantages of high abundance, reproducibility, safe storage and distribution, no toxicity, low price, relatively high energy density and the like, and is a promising fuel. One option for converting glucose into electrical energy is fuel cell technology. However, the widespread use of noble metal catalyzed (Au, pt, pd and metal alloys thereof) fuel cells has raised concerns about expensive, limited, non-replaceable noble metal resources. In addition, these catalysts typically require basic conditions and high temperatures to increase the oxidation rate. Enzyme biofuel cells (EBFCs) are capable of directly converting chemical energy of various biofuels into electrical energy under mild conditions (ambient temperature and neutral pH) by either anodic catalytic fuel oxidation or cathodic catalytic oxidant reduction by the catalytic activity of biological enzymes. In addition, EBFCs have the advantage of catalyst regeneratability and fuel diversity using bio-enzyme catalysts.
The collection of electrons generated in the bioelectrocatalytic reaction between the oxidoreductase and its substrate at the electrode surface is critical for EBFCs. In some cases, the enzyme is capable of passing electricityThe polar surface undergoes Direct Electron Transfer (DET). DET allows operation with little overpotential due to the inherent nature of the enzyme. However, it requires a strict orientation of the enzyme molecules, and the electrode surface can only be attached to one layer of enzyme at the same time at most. In most cases, DET between the enzyme and the electrode is very difficult due to the large size and spatial structure of the enzyme. In particular, when the redox active center of the enzyme is buried deep inside the insulating protein. In this case, the electroactive molecule is used as a redox mediator, establishing electronic communication between the enzyme cofactor and the electrode surface, a mechanism known as indirect electron transfer (MET). For example, ferrocenyl compounds, tetrathiafulvalene, naphthoquinone, 1-methoxy-5-methylphenoxazin methyl sulfate, methylene blue and 1, 4-benzoquinone, which are commonly used as redox mediators for shuttling electrons in the anodic oxidation of biofuels such as glucose and lactic acid. Unfortunately, these mediators are unable to oxidize glucose. Only 2e during oxidation of a single anodic enzyme catalytic system - Transfer, so that most of the energy remains in the oxidation product of glucose. Therefore, the development of novel electronic media capable of catalyzing glucose oxidation is of great importance for the development of glucosyl EBFCs.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. To this end, it is an object of the present invention to provide an anode catalyst for a fuel cell and a glucose fuel cell capable of mediating electron transfer between the redox centres of glucose oxidase and/or glucose dehydrogenase and the electrode surface using 2, 6-tetramethyl-1-piperidino-N-oxy (TEMPO). Meanwhile, TEMPO can oxidize glucose into glucuronic acid under mild condition to realize glucose 4e - The oxidized complex enzyme-organic cascade (HEOC) system improves the catalytic efficiency of glucose oxidation, and makes TEMPO a promising alternative catalyst for glucose oxidation in the application of bioelectronics.
To this end, a first aspect of the present invention provides an anode catalyst for a fuel cell. According to an embodiment of the present invention, the anode catalyst includes:
glucose oxidase and/or glucose dehydrogenase;
and TEMPO or a derivative thereof.
Enzymatic biofuel cells (EBFCs) are a better method of converting chemical energy into electrical energy. However, in most cases, direct Electron Transfer (DET) between the active center of the enzyme and the electrode surface is difficult to occur. DET allows operation with little overpotential due to the inherent nature of the enzyme. However, it requires a strict orientation of the enzyme molecules, and the electrode surface can only be attached to one layer of enzyme at the same time at most. In most cases, DET between the enzyme and the electrode is very difficult due to the large size and spatial structure of the enzyme. In particular, when the redox active center of the enzyme is buried deep inside the insulating protein. In this case, the electroactive molecule is used as a redox mediator, establishing electronic communication between the enzyme cofactor and the electrode surface, a mechanism known as indirect electron transfer (MET). Whereas the commonly used redox mediators are not capable of oxidizing glucose directly. The inventors have found that in a fuel cell with glucose as electrolyte, electron transfer between the redox centre and the electrode surface of glucose oxidase and/or glucose dehydrogenase can be mediated by TEMPO or a derivative thereof. When Glucose Oxidase (GO) X ) And/or glucose dehydrogenase oxidizes glucose, electron transfer occurs, and electrons are taken up by GO X Is taken away from the active center of (C), but GO X The self protein structure limits the transfer of electrons of the active center to the electrode, while TEMPO is taken as a redox medium and can assist in electron transfer, and is positioned at GO X Electrons of the redox active sites are mediated onto the electrodes, creating a potential difference.
TEMPO (2, 6-tetramethyl-1-piperidin-N-oxy) and its related nitroxide derivatives are an important class of organic oxidation catalysts that oxidize various alcohols and aldehydes in mild aqueous solutions at room temperature in industrial and laboratory applications. The inventors have also found that TEMPO is also capable of deeply oxidizing glucose. In a single GO X Only 2e in the oxidation process of the catalytic system - Transfer, GO X Catalytic oxidation of glucose to form gluconic acidWhereas gluconic acid can be oxidized by TEMPO to glucuronic acid, thereby achieving 4e - And (5) transferring. By GO X Compared with single GO as anode catalyst of fuel cell by TEMPO or its derivative X The catalytic efficiency of glucose oxidation can be further improved. While TEMPO alone can also catalyze the oxidation of glucose, its catalysis is electrocatalytic and the reaction efficiency is much lower than that of an enzyme catalyzed reaction.
According to an embodiment of the present invention, the above anode catalyst may further include at least one of the following additional technical features:
according to an embodiment of the invention, the derivative of TEMPO is selected from CH 3 O-TEMPO, HO-TEMPO, HOOC-TEMPO and CH 3 At least one of CONH-TEMPO.
According to an embodiment of the invention, the glucose oxidase and/or glucose dehydrogenase are/is attached to the surface of the anode carrier of the fuel cell, and the activity of the glucose oxidase and/or glucose dehydrogenase on the anode carrier per unit area is 10-30U/cm 2 . The enzyme activity of glucose oxidase and/or glucose dehydrogenase attached to the anode carrier in unit area is 10-30U/cm 2 Under the condition, the glucose oxidation catalysis efficiency can be further improved. If the enzyme activity per unit area on the anode carrier is further improved, the enzyme activity per unit area is more than 30U/cm 2 The diffusion resistance of TEMPO on the electrode surface is increased, thereby reducing the catalytic efficiency.
According to an embodiment of the present invention, the TEMPO or a derivative thereof is dissolved in the electrolyte of the fuel cell, and the TEMPO or a derivative thereof has a concentration of 0.5 to 5mM. The concentration of TEMPO or its derivative is 0.5-5 mM, and this can raise the catalytic efficiency of glucose oxidation and promote electron transfer. Too low a concentration of TEMPO or its derivatives may lead to a decrease in the catalytic current. Beyond this range, the catalytic current does not increase significantly even if the TEMPO concentration is further increased.
According to an embodiment of the invention, the TEMPO or derivative thereof has a concentration of 1-2 mM.
In a second aspect, the invention provides a glucose fuel cell. According to an embodiment of the invention, the glucose fuel cell comprises the anode catalyst of the first aspect.
According to an embodiment of the present invention, the glucose fuel cell further comprises an anode, an electrolytic cell and a cathode, the anode comprises an anode carrier and the anode catalyst, wherein glucose oxidase and/or glucose dehydrogenase in the anode catalyst is attached to the surface of the anode carrier, and the activity of the glucose oxidase and/or glucose dehydrogenase on the anode carrier per unit area is 10-30U/cm 2 。
According to an embodiment of the invention, the electrolytic cell comprises a glucose electrolyte solution in which the TEMPO or a derivative thereof is dissolved, the TEMPO or a derivative thereof having a concentration of 0.5 to 5mM.
According to an embodiment of the invention, the TEMPO or derivative thereof has a concentration of 1-2 mM. This can further improve the catalytic efficiency of glucose oxidation.
According to an embodiment of the invention, the anode catalyst is used for catalytic oxidation of glucose electrolyte solution in the electrolytic cell at a pH of 6-8.
According to an embodiment of the present invention, the concentration of glucose in the glucose electrolyte solution is 5 to 200mM, preferably 50 to 100mM. Thus, the catalytic current can be maintained in a suitable range, and if the glucose concentration is too low, the catalytic current is low, whereas if the glucose concentration exceeds 200mM, the catalytic current does not increase significantly even if the glucose concentration is increased.
According to the embodiment of the invention, the anode carrier is a glassy carbon electrode, and the glassy carbon electrode is further modified by a nitrogen doped graphene-carbon nanotube composite material (N-RGO@CNTs).
According to the embodiment of the invention, the anode of the glucose fuel cell is a continuous net-shaped N-doped graphene-carbon nano tube composite material modified Glassy Carbon Electrode (GCE) with high graphitization degree, and the anode has higher electric activity area and faster electron transfer dynamics capability than a bare GCE.
According to an embodiment of the invention, the cathode comprises a cathode carrier and a cathode catalyst, wherein the cathode carrier is carbon felt or carbon cloth, and the cathode catalyst is platinum-based metal.
According to an embodiment of the invention, the anode and the cathode of the glucose fuel cell are separated by an ion exchange membrane.
A third aspect of the invention provides the use of the anode catalyst of the first aspect, the glucose fuel cell of the second aspect, in the manufacture of a biofuel cell.
The present invention provides a mixed enzyme and organic cascade (HEOC) system consisting of a biocatalyst glucose oxidase (GOx) and/or glucose dehydrogenase and an electro-mechanical catalyst TEMPO for enhancing glucose oxidation. Electrochemical tests show that TEMPO can be used as an electrocatalyst for catalyzing 4e of glucose under neutral condition - Oxidation, which also serves as a redox mediator, shuttles electrons between the GOx and the electrode surface, thereby significantly increasing the catalytic efficiency of the cascade. glucose/O built using HEOC anode and respiratory Pt cathode 2 EBCFs provided 38.1. Mu.W.cm -2 651.4. Mu.A.cm -2 Is provided. The method can be used for preparing a novel high-efficiency energy conversion system, and is suitable for energy conversion of various substrates such as sugar, alcohol and the like.
A fourth aspect of the invention provides a micro power supply. According to an embodiment of the invention, the micro power supply comprises the anode catalyst of the first aspect and/or the glucose fuel cell of the second aspect.
A fifth aspect of the invention provides a bioelectronic device. According to an embodiment of the invention, the bioelectronic device comprises a glucose fuel cell according to the second aspect.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
GCE is shown in FIG. 1 (A)Representative CV curves in 0.1M PBS at pH 7.0, "a" is TEMPO-free, glucose-free; "b" is TEMPO-free, 50mM glucose; "c" is 1mM TEMPO, glucose free; "d" is 1mM TEMPO,50mM glucose; (B) A representative CV curve of GCE in 0.1M PBS at pH 7.0 is shown, "a" being TEMPO-free, gluconolactone-free; "b" is TEMPO-free, 50mM gluconolactone; "c" is 1mM TEMPO, no gluconolactone; "d" is 1mM TEMPO,50mM gluconolactone. The scanning rate was 10 mV.s -1 ；
FIG. 2 shows a representative CV curve of GCE in 0.1M PBS at pH 7.0; wherein, "a" is 1mM TEMPO, with no glucuronic acid; "b" is 1mM TEMPO,50mM glucuronic acid;
FIG. 3 shows representative CV curves of GCE in 0.1M PBS (containing 1mM TEMPO) at various pH values to achieve glucose-free, dashed lines containing 50mM glucose;
in FIG. 4 (A) there is shown GOx (curve a), N-RGO@CNTs (curve b), GOx/N-RGO@CNTs (curve c) modified GCE in N 2 CV curve in saturated 0.1M PBS (pH 7.0). GOx/N-RGO@CNTs modified GCE in N 2 CV curve (curve d) after addition of 50mM glucose in saturated 0.1M PBS (pH 7.0); (B) Shows that GOx/N-RGO@CNTs modified GCE is modified in N 2 Saturated 0.1M PBS (pH 7.0, containing 1mM TEMPO) did not contain glucose (curve a) and CV curves in 50mM glucose (curve b), sweeping at a rate of 10 mV.s -1 The method comprises the steps of carrying out a first treatment on the surface of the (C) Shows GOx (curve a), N-RGO@CNTs (curve b), GOx/N-RGO@CNTs (curve c) modified GCE in N 2 Chronoamperometric curves after continuous addition of glucose in saturated 0.1M PBS (pH 7.0); (D) Shows the relation of the catalytic current of GOx/N-RGO@CNTs modified GCE along with the change of glucose concentration;
FIG. 5 (A) shows that GOx/N-RGO@CNTs modified GCE is N at different scanning speeds 2 CV curve in saturated 0.1M PBS (pH 7.0); (B) shows the variation of peak current density with sweep rate;
FIG. 6 shows that GOx/N-RGO@CNTs modified GCE is at O 2 CV curve (curve a) in saturated 0.1M PBS (pH 7.0) after 50mM glucose (curve b) was added, sweep speed was 10 mV.s -1 ；
In FIG. 7A) Showing GCE at N 2 LSV curve in saturated 0.1M PBS (pH 7.0); (B) Showing GCE at N 2 CV curve in saturated 0.1M PBS (pH 7.0, containing 1mM TEMPO);
FIG. 8 shows that GDH/N-RGO@CNTs modified GCE is N 2 Saturated 0.1M PBS (pH 7.0, containing 1mM TEMPO) did not contain glucose (curve a) and CV curves in 50mM glucose (curve b), sweeping at a rate of 10 mV.s -1
FIG. 9 shows a mass spectrum of the mixed enzymatic/electro-mechanically catalyzed glucose oxidation electrolysis product of example 3;
FIG. 10 (A) is a schematic view showing the structure of a glucose biofuel cell in example 4; (B) shows a polarization curve and a power output curve.
Detailed Description
The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The term "optionally" is used for descriptive purposes only and is not to be construed as indicating or implying relative importance. Thus, a feature defined as "optional" may explicitly or implicitly include or exclude that feature.
According to a specific embodiment of the present invention, there is provided an anode catalyst for a fuel cell, comprising:
glucose oxidase and/or glucose dehydrogenase; and
TEMPO or a derivative thereof.
Derivatives of TEMPO include, but are not limited to, CH 3 O-TEMPO, HO-TEMPO, HOOC-TEMPO and CH 3 CONH-TEMPO has the formula:
according to a specific embodiment of the present invention, there is provided a glucose fuel cell comprising an anode, an electrolytic cell and a cathode, the anode comprising an anode carrier and an anode catalyst, wherein glucose oxidase and/or glucose dehydrogenase in the anode catalyst is/are attached to the surface of the anode carrier, and the activity of the glucose oxidase and/or glucose dehydrogenase per unit area of the anode carrier is 10 to 30U/cm 2 . TEMPO or a derivative thereof is dissolved in a glucose electrolyte solution in an electrolytic cell. The anode catalyst is used for catalytically oxidizing the glucose electrolyte solution in the electrolytic cell at a pH of 6-8. The concentration of glucose in the glucose electrolyte solution is 5 to 200mM, preferably 50 to 100mM, and more preferably 50mM.
According to a specific embodiment of the invention, the TEMPO or derivative thereof is present in a concentration of 0.5 to 5mM, preferably 1 to 2mM.
According to a specific embodiment of the invention, the anode carrier is a glassy carbon electrode, which is further modified with N-RGO@CNTs.
According to a specific embodiment of the invention, the cathode comprises a cathode support and a cathode catalyst, the cathode support being a carbon felt or carbon cloth and the cathode catalyst being a platinum-based metal, such as a Pt/C electrode.
According to an embodiment of the invention, the anode and the cathode of the glucose fuel cell are separated by an ion exchange membrane. The ion exchange membrane may be, for example, a Nafion membrane, such as Nafion117 membrane. According to an embodiment of the present invention, there is provided a bioelectronic device including the glucose fuel cell, for example, a self-powered glucose biosensor, which can be used for detecting glucose concentration in human sweat, urine, and other excretions.
It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1: TEMPO-mediated electrocatalytic oxidation test of glucose
1. TEMPO-mediated electrocatalytic CV test and pH range assay for glucose
Pt foil (1 cm) with Ag/AgCl (saturated KCl solution) as reference electrode 2 ) For counter electrode, a glassy carbon electrode (GCE, diameter 3 mm) was used as the working electrode and TEMPO electrocatalytic oxidation of glucose was characterized using Cyclic Voltammetry (CV) in 0.1M PBS (pH 7.0). 10 mV.s were recorded in 0.1mM PBS (pH 7.0) with CHI 660E electrochemical workstation in the presence and absence of 50mM glucose -1 Containing 1mM TEMPO. Control experiments CV testing was performed with 50mM glucose added in the absence of TEMPO. The pH range was determined by CV with 1mM TEMPO and 50mM glucose in 0.1M PBS with pH range 5 to 10.
2. Experimental results
The ability of TEMPO to electrocatalytic glucose oxidation was investigated using CV. FIG. 1 (A) shows that in the absence and presence of glucose, the concentration of glucose in PBS was 1 mV.s at pH 7.0 in 0.1M -1 CV curve of sweep speed. From the figure, a characteristic reversible redox peak of TEMPO can be observed (curve c), wherein the oxidation peak current of TEMPO radical oxidation to oxyammonia ion occurs at 560mV (vs. ag/AgCl). When 50mM glucose was added to the solution, the current density increased to 98. Mu.A.cm at 560mV (vs. Ag/AgCl) -2 (curve d). In the absence of TEMPO or glucose, there is no discernable catalytic signal in CV (curves a and b), indicating that the catalytic current is generated by TEMPO catalyzing glucose oxidation. The enzymatic oxidation product of glucose is typically gluconolactone. CV testing was then performed in 0.1M PBS at pH 7.0 (containing 1mM TEMPO) in the absence and presence of gluconolactone to verify the ability of TEMPO to electrically catalyze the deep oxidation of glucose. As shown in FIG. 1 (B), a characteristic reversible redox peak of TEMPO (curve c) can be observed. When 50mM glucolactone was added to the solution, the current density was at 56Increasing to 86. Mu.A.cm at 0mV (vs. Ag/AgCl) -2 (curve d). In the absence of TEMPO or gluconolactone, there is no discernable signal in CV (curves a and b), indicating that TEMPO has the ability to catalyze the oxidation of gluconolactone, while TEMPO has the ability to catalyze glucose 4e - Oxidizing power. TEMPO may preferentially oxidize primary hydroxyl groups due to the sterically hindered nature of secondary hydroxyl groups, due to hydrolysis of gluconolactone to gluconic acid, and the presence of primary hydroxyl groups in both products. Thus, further oxidation of gluconolactone or gluconic acid with glucose oxidation to glucuronic acid results in glucose 4e - And (5) oxidizing. However, after 50mM glucuronic acid was added to the buffer, no catalytic current was shown at 560mV (vs. Ag/AgCl) (FIG. 2), indicating that TEMPO was unable to further oxidize glucuronic acid under the same conditions.
The electrocatalytic efficiency of TEMPO for glucose oxidation is related to the pKa of hydroxylamine intermediates produced by the electrocatalytic reaction of TEMPO, glucose and their oxidation products. The hydroxylamine intermediate requires deprotonation/oxidation to regenerate the radical form. FIG. 3 depicts the effect of solution pH on TEMPO electrocatalytic oxidation of glucose. The reduced activity at acidic pH indicates that the acidic environment no longer promotes the coupled deprotonation/oxidation of the hydroxylamine intermediate, since the pH at acidic environment is much lower than the pKa of TEMPO hydroxylamine, 7.34. However, when the pH is below the pKa of TEMPO hydroxylamine, the catalytic signal is still evident, indicating that TEMPO can work with GOx, which typically works under neutral conditions. Under alkaline conditions, as the pH of the solution increases to 8.0 and 9.0, the catalytic current increases significantly, probably due to the kinetic enhancement of the counter-disproportionation of hydroxylamine intermediates and oxyammonia ions to TEMPO radicals.
Example 2: bioelectric catalytic testing of GOx on glucose
1. GOx-mediated electrocatalytic CV test of glucose
The bioelectrical catalytic oxidation of glucose by GOx was studied using CV. CV test under N 2 Saturated 0.1M PBS (pH 7.0) with and without 50mM glucose, at a scan rate of 10 mV.s -1 . Wherein N-RGO@CNTs (N-doped graphene@carbon nanotubes) (N-RGO@CNTs preparedReference is made to "j.mate.chem.a, 2019,7,11077-1085") composite as carrier material for securing GOx to GCE. For the preparation of GOx-modified electrodes, 20. Mu. L N-RGO@CNTs dispersion (10 mg. ML -1 Ultrasonic dispersion in ultra pure water) and 20. Mu.L of GOx solution (30 mg. Multidot.mL -1 Dissolved in 0.1m pbs, ph 7.0) was mixed by vortex shaking. Then 5. Mu.L of the mixture was cast onto the polished GCE surface and stored in a refrigerator at 4℃until the water evaporated completely. Finally, 5. Mu.L of 0.5% Nafion solution (purchased from Sigma) was cast on the GOx/N-RGO@CNTs modified GCE electrode, and stored in a refrigerator at 4℃until the water was evaporated completely. Glucose Dehydrogenase (GDH)/N-RGO@CNTs modified GCE was prepared using a process similar to GOx. In contrast, GOx-modified GCE and N-RGO@CNTs-modified GCE were prepared by casting. Finally, 5 mu L of 0.5% Nafion solution is respectively cast on GOx modified GCE and N-RGO@CNTs modified GCE, and the mixture is put into a refrigerator and stored at 4 ℃ until the water is evaporated completely.
2. Experimental results
GOx is often used as a biocatalyst to prepare biosensors and EBFCs. To verify that GOx/N-RGO@CNTs modified GCE catalyzes the glucose oxidation capacity, in N 2 CV testing was performed in saturated 0.1M PBS (pH 7.0). The CV curves of typical GOx and N-RGO@CNTs modified GCE in the absence of glucose (curve a) and in the presence of glucose (curve b) are shown in FIG. 4 (A). Both CV curves show featureless voltammetric characteristics. For GOx/N-RGO@CNTs modified GCE, a background/capacitive current derived from N-RGO@CNTs carrier material and a pair of reversible redox peaks (curve c) with a surface potential of-0.44V can be detected, which is in comparison with GOx cofactor FAD/FADH 2 Is very close (about-0.45V vs. Ag/AgCl). The symmetrical shape of the peaks and the ratio of peak current to potential scan rate (fig. 5) indicate that the electrode process of redox current from electroactive species adsorbed on the surface of N-rgo@cnts is a quasi-reversible surface control behavior. It was shown that in order to establish electrical contact between the active center of GOx and the electrode surface, a modification of the N-RGO@CNTs support material had to be performed on the electrode surface.
To N 2 Modification of GOx/N-RGO@CNTs by adding 50mM glucose into saturated solutionThe CV curve of GCE of (a) has no effect (fig. 4 (a), curve d), indicating that DET-free bioelectrocatalysis occurs. This is due to the large size of GOx (average diameter 8 nm) and the deep buried active centers making it very difficult to achieve DET bioelectrocatalysis between the active center and the electrode surface.
Comparative experiments in O 2 Saturated 0.1M PBS (pH 7.0) was used as shown in FIG. 6. The superposition of the reduction currents is due to O 2 Is (FAD+2H) + +2e - →FADH 2 ). 50mM glucose was added to O 2 After saturation in the buffer, the cathode current decreases significantly, mainly due to O 2 Is consumed in mediating the enzymatic glucose oxidation process, resulting in O 2 Reduction current is reduced, O 2 The mediated GOx catalyzed glucose oxidation equation is shown in formula 1. Thus, the above results indicate that GOx is immobilized on N-RGO@CNTs in the presence of O 2 The enzyme catalytic activity is maintained for the substrate glucose.
Wherein, glucsoe is glucose, and gluconolactone is glucolactone.
Equation (1) represents the MET mode of GOx-catalyzed glucose oxidation, where GOx catalyzes glucose oxidation and is oxidized by O 2 Recycling to generate H 2 O 2 . However, H 2 O 2 The electrochemical detection of (a) requires a high overpotential (oxidation potential>+0.65V, reduction potential<-1.7V vs. standard hydrogen electrode), which limits the analytical applications. On the other hand, H in solution 2 O 2 The presence of (c) has an adverse effect on the operation stability of GOx, which can reduce the performance of the device. It should be noted that TEMPO is capable of mediating H at relatively low overpotential 2 O 2 As shown in fig. 7, which makes TEMPO a highly sensitive and selective biosensor promising.
Example 3: hybrid enzymatic/electro-mechanical catalytic glucose oxidation test
1. Hybrid enzymatic/electro-mechanically catalyzed glucose oxidation CV test
Enzyme catalysis and organic electrocatalytic composite oxidation are carried out on glucose by adopting CV and a chronoamperometry. CV test on N containing 1mM TEMPO 2 In the presence and absence of 50mM glucose in saturated 0.1mM PBS (pH 7.0), at 10 mV.s -1 Is performed at a sweeping speed. Chronoamperometry is a continuous addition of glucose to N at an applied potential of 0.5V 2 Saturated 0.1M PBS (pH 7.0). Control experiments were performed in the same buffer without TEMPO or GOx. Pt foil (1 cm) with Ag/AgCl (saturated KCl solution) as reference electrode 2 ) The GOx/N-RGO@CNTs modified GCE is used as a working electrode, wherein the GOx dosage is 20U/cm 2 If GDH/N-RGO@CNTs modified GCE is used as a working electrode, the GDH dosage is 20U/cm 2 The electrolysis experiments were performed in 0.1M PBS at pH 7.0. The applied potential of the electrolysis experiment was 0.8V (vs. Ag/AgCl), and the electrolysis time was 72h. The oxidation products were qualitatively analyzed by mass spectrometry on a Thermo Fisher Scientific LTQ FT Utra (ESI) mass spectrometer.
2. Experimental results
The apparent potential of TEMPO is 0.53V (vs. Ag/AgCl) which is far higher than that of active center FAD/FADH of GOx 2 According to the Nernst equation, TEMPO mediated redox reactions of GOx are thermodynamically favourable. In addition, TEMPO also has the ability to deeply oxidize glucose, which makes it have a broad application prospect in EBFCs. We used the CV test to explore the feasibility of TEMPO-mediated GOx-catalyzed glucose oxidation in anaerobic 0.1M PBS at pH 7.0 (fig. 4 (B)). CV curve (0.29 mA.cm at 560 mV) with GOx/N-RGO@CNTs modified GCE in the absence of glucose -2 Ag/AgCl, curve a compares, GOx/N-RGO@CNTs modified GCE shows 3.25 mA.cm at 560mV (vs. Ag/AgCl) in the presence of 50mM glucose -2 Is shown to be capable of shuttling electrons between the GOx active center and the electrode surface. In addition, TEMPO was also able to mediate electron transfer between FAD-dependent GDH and electrode surface (fig. 8), further demonstrating the potential significance of TEMPO in bioelectronic applications.
FIG. 4 (C) shows GOx/N-RGO@CNTs modified GCE under stirring at an applied potential of 0.5V (vs. Ag/AgCl) 2 Chronoamperometric response of continuous addition of glucose in saturated 0.1M PBS (pH 7.0). In the absence of 1mM TEMPO, no catalytic signal was observed for GOx/N-RGO@CNTs modified GCE (curve a). Glucose was continuously added to a solution containing 1mM TEMPO and a weak current signal was detected by the N-RGO@CNTs modified GCE (curve b). When glucose was added to a buffer containing 1mM TEMPO, the oxidation current of GOx/N-RGO@CNTs modified GCE was significantly increased (curve c). Each successive addition of glucose causes the oxidation current to increase within 3s and then reach steady state current, indicating that the constructed HEOC system has a rapid response capability to glucose. The oxidation current showed a linear increase with increasing glucose addition, and the linear correlation coefficient (R) was 0.9999. When the glucose concentration was increased to 30mM, a saturation catalytic current could be detected, indicating that TEMPO catalyzed glucose showed typical Michaelis-Menten enzyme reaction kinetics. To determine the oxidation products of glucose, an electrolysis experiment was performed at room temperature in 0.1M PBS at pH 7.0 and the main products were studied by mass spectrometry. The mass spectral results shown in FIG. 9 demonstrate that the electrolyte products are predominantly gluconic acid and glucuronic acid, demonstrating HEOC system mediated glucose 4e - Oxidation pathway.
Example 4: biofuel cell assembly and testing
And the GOx/N-RGO@CNTs modified GCE is taken as an anode, and the cathode is carbon cloth with one surface coated with a Pt/C catalyst layer. A carbon-based layer and a PTFE diffusion layer are coated on opposite sides of the Pt/C catalyst layer. The anode and the cathode are separated by a Nafion117 membrane. The electrolyte was N2 saturated 0.1M PBS (pH 7.0) in which 50mM glucose and 1mM TEMPO were dissolved. The performance of BFCs was evaluated by Linear Sweep Voltammetry (LSV) at a sweep rate of 1 mV.s -1 。
To verify the viable application of the HEOC system in EBFC, the present invention prepares and tests glucose/O 2 EBFC, TEMPO and glucose were dissolved in 0.1M PBS as electrolytes, GOx/N-RGO@CNTs modified GCE as anode and Pt/C as cathode (A in FIG. 10). In the anodic oxidation of glucose, TEMPO is used as a glucoseA catalyst for the deep oxidation of sugars while establishing electronic communication as a mediator between the GOx active center and the electrode surface. Electrons generated by anodic oxidation of glucose are transported to the Pt/C cathode by an external circuit, while the generated protons pass through the Nafion membrane to the cathode. On the cathode side, electrons are transferred from the carbon cloth to the Pt/C catalyst, O in air 2 Through PTFE diffusion layer and carbon cloth, the catalyst enters Pt/C catalyst and finally is reduced into H 2 O. Constructed glucose/O 2 EBFC has 1 mV.s -1 Can produce 38.1 mu W cm with 50mM glucose -2 Maximum power density of 651.4. Mu.A.cm -2 (B in fig. 10). glucose/O when TEMPO is not present 2 The maximum power density of the EBFC was 3.3. Mu.W.cm -2 Maximum current density of 35.6. Mu.A.cm -2 The presence of TEMPO has been shown to significantly improve the energy conversion efficiency of fuel cells.
The invention provides a new strategy for glucose oxidation under neutral conditions. The cascade of enzyme and organic catalyst can synergistically catalyze the deep oxidation of glucose to produce 2.96mA cm -2 Catalytic current density of (a). Furthermore, by constructing glucose/O consisting of HEOC anode and Pt/C cathode 2 EBFCs, the feasibility of the proposed HEOC system for applications in EBFCs was verified. The obtained glucose/O 2 The maximum power density of the EBFC was 38.1. Mu.W.cm -2 Maximum current density of 651.4. Mu.A.cm -2 This is due to the use of dual function TEMPO: (1) 4e of catalytic glucose - Oxidizing; (2) improving energy conversion efficiency as a mediator of GOx. Thus, the HEOC system proposed by the present invention provides the potential for developing a more efficient energy conversion system.
In the description of the present specification, the descriptions of the terms "one embodiment," "some embodiments," "examples," "particular examples," "some embodiments," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (17)
1. An anode catalyst for a fuel cell, comprising:
glucose oxidase and/or glucose dehydrogenase; and
TEMPO or derivatives thereof;
wherein the glucose oxidase and/or glucose dehydrogenase is attached to the anode support surface of the fuel cell.
2. Anode catalyst according to claim 1, characterized in that the derivative of TEMPO is selected from CH 3 O-TEMPO, HO-TEMPO, HOOC-TEMPO and CH 3 At least one of CONH-TEMPO.
3. The anode catalyst according to claim 1, wherein the activity of glucose oxidase and/or glucose dehydrogenase on the anode carrier per unit area is 10 to 30u/cm 2 ；
And the TEMPO or the derivative thereof is dissolved in the electrolyte of the fuel cell, and the concentration of the TEMPO or the derivative thereof is 0.5-5 mM.
4. The anode catalyst according to claim 3, wherein the TEMPO or derivative thereof has a concentration of 1 to 2mm.
5. A glucose fuel cell comprising the anode catalyst of any one of claims 1 to 4.
6. The glucose fuel cell according to claim 5, further comprising an anode, an electrolytic cell and a cathode, wherein the anode comprises an anode carrier and the anode catalyst, wherein glucose oxidase and/or glucose dehydrogenase in the anode catalyst is attached to the surface of the anode carrier, and the activity of the glucose oxidase and/or glucose dehydrogenase on the anode carrier per unit area is 10-30 u/cm 2 。
7. The glucose fuel cell of claim 6, wherein the electrolytic cell comprises a glucose electrolyte solution in which TEMPO or a derivative thereof is dissolved, the TEMPO or derivative thereof having a concentration of 0.5 to 5mm.
8. The glucose fuel cell of claim 7, wherein the TEMPO or derivative thereof has a concentration of 1-2 mm.
9. The glucose fuel cell of claim 7 or 8, wherein the anode catalyst is used to catalyze the oxidation of glucose electrolyte solution in the electrolytic cell at a pH of 6-8.
10. The glucose fuel cell according to claim 7 or 8, wherein the concentration of glucose in the glucose electrolyte solution is 5 to 200mm.
11. The glucose fuel cell according to claim 7 or 8, wherein the concentration of glucose in the glucose electrolyte solution is 50-100 mm.
12. The glucose fuel cell of claim 6, wherein the anode carrier is a glassy carbon electrode further modified with a nitrogen doped graphene-carbon nanotube composite.
13. The glucose fuel cell of claim 6, wherein the cathode comprises a cathode support and a cathode catalyst, the cathode support being a carbon felt or carbon cloth, the cathode catalyst being a platinum-based metal.
14. The glucose fuel cell of claim 6, wherein the anode and cathode of the glucose fuel cell are separated by an ion exchange membrane.
15. Use of the anode catalyst of any one of claims 1 to 4, the glucose fuel cell of any one of claims 5 to 14 in the manufacture of a biofuel cell.
16. A micro power supply comprising the anode catalyst of any one of claims 1 to 4 and/or the glucose fuel cell of any one of claims 5 to 14.
17. A bioelectronic device comprising a glucose fuel cell as claimed in any one of claims 5 to 14.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| WO2021075816A1 (en) * | 2019-10-15 | 2021-04-22 | 박용학 | Microbial fuel cell using electron absorber having high reduction potential, and method of generating electric energy using same |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014167063A1 (en) * | 2013-04-10 | 2014-10-16 | Sergey Shleev | Charge-storing fuel cell |
| WO2020105002A1 (en) * | 2018-11-23 | 2020-05-28 | King Abdullah University Of Science And Technology | Polymeric enzyme-based biofuel cell and methods of making and using |
| WO2021075816A1 (en) * | 2019-10-15 | 2021-04-22 | 박용학 | Microbial fuel cell using electron absorber having high reduction potential, and method of generating electric energy using same |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Deep oxidization of glucose driven by 4-acetamido-TEMPO for a glucose fuel cell at room temperature;Gangyong Li等;《ChemComm》;20210309;第4052-4054页 * |
| 漆酶的生物电化学研究;赵丹;王炎;赵敏;;化学进展(06);全文 * |
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