A methyl viologen-dopamine polymer enzyme-mimicking catalytic electrode, a preparation method and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SOUTH CHINA NORMAL UNIV
- Filing Date
- 2023-04-21
- Publication Date
- 2026-06-09
AI Technical Summary
In existing glucose fuel cells, precious metal catalysts are expensive, enzyme catalysts are unstable, methyl viologen is not suitable as a cathode material, and dopamine polymers cannot directly catalyze glucose oxidation, resulting in limited performance.
A methyl viologen-dopamine polymeric enzyme catalytic electrode was prepared by a continuous cyclic voltammetry-driven method. The composite material was formed by co-assembling methyl viologen and dopamine on the substrate electrode and used as the anode and cathode of a glucose fuel cell to improve the oxygen catalytic reduction activity.
The prepared electrode exhibits high open-circuit voltage and power density in glucose fuel cells, simplifies catalyst use, reduces costs, and is environmentally friendly.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of fuel cell technology, specifically relating to a methyl viologen-dopamine polymer enzyme-mimicking catalytic electrode, its preparation method, and its application in glucose fuel cells. Background Technology
[0002] To address global warming caused by traditional energy sources, countries are vigorously developing new and environmentally friendly energy sources. Among these, the glucose fuel cell, a primary battery device that converts the biomass energy of glucose into electrical energy, has attracted widespread attention and research due to its high conversion efficiency and clean, environmentally friendly nature. The process involves glucose oxidation at the anode to produce gluconic acid, and oxygen reduction at the cathode to produce water. The performance of the glucose fuel cell is primarily influenced by the catalysts at the anode and cathode. Glucose catalysts are mainly classified into noble metal catalysts, enzyme catalysts, and enzyme-mimicking catalysts.
[0003] Among them, Pt-based catalysts are highly efficient for the catalytic oxidation of glucose, but their high resource cost leads to high costs. Enzyme catalysts are highly efficient and specific for the catalytic oxidation of glucose, but they are highly unstable due to the influence of temperature and pH. Therefore, designing and developing novel enzyme-mimicking catalysts based on the structure of enzyme catalysts is of great significance in the research of glucose fuel cells.
[0004] Methyl viologen (MV 2+ Methyl viologen is dimethyl bipyridine, possessing excellent redox properties. A reversible redox reaction can be achieved through electrochemical and photochemical methods, accompanied by rich color changes. Methyl viologen exists in three different redox states. The neutral viologen V exhibits both monovalent and divalent cation states when a voltage is applied. Its divalent cation V... 2+ It is the most stable, colorless, and has a monovalent cation V. + Methyl viologen carries a non-localized positive charge that can transfer between +1 and 0 valence N atoms. This charge transfer causes a color change; the higher the molar absorptivity, the deeper and more intense the color. In microbial fuel cells, methyl viologen is used as a redox mediator to facilitate electron transfer from microbial cells to the current-collecting electrode. It has also been studied as a non-noble metal catalyst in homogeneous electrocatalysis for alkaline glucose fuel cells. However, methyl viologen has an excessively negative catalytic reduction potential for oxygen; a more positive catalytic reduction potential for oxygen is more beneficial to the performance of glucose fuel cells. Therefore, methyl viologen is unsuitable as a cathode material for glucose fuel cells.
[0005] Dopamine (DA) exists as a cationic compound in tissues and body fluids and is an important catecholamine neurotransmitter. It can polymerize into polydopamine (PDA) monomers. Currently, there is considerable research on the application of DA as a catalyst in fuel cells, primarily focusing on DA-mediated electrochemical oxidation of ascorbic acid and its enhancement of glucose catalytic oxidation by glucose oxidase or metal nanoparticles. Some studies have also shown that PDA can synergistically electrocatalyze the oxidation of ascorbic acid and glucose, and can catalytically reduce oxygen; however, PDA cannot yet directly catalytically oxidize glucose. Summary of the Invention
[0006] To address the shortcomings and deficiencies of existing technologies, the primary objective of this invention is to provide a method for preparing a methyl viologen-dopamine polymer-based enzyme-mimetic catalytic electrode. This method aims to increase the active sites of the reaction by introducing polydopamine, thereby enhancing the catalytic reduction of oxygen and preparing a composite electrode material with dual-function catalysis for application in neutral glucose fuel cells.
[0007] Another object of the present invention is to provide a methyl viologen-dopamine polymer enzyme-mimicking electrode prepared by the above preparation method.
[0008] Another object of the present invention is to provide an application of the above-mentioned methyl viologen-dopamine polymer enzyme-mimicking electrode in a glucose fuel cell.
[0009] The objective of this invention is achieved through the following technical solution:
[0010] A method for preparing a methyl viologen-dopamine polymer-based enzyme-mimicking electrode includes the following steps: using a 0.2 mmol / L... -1 A methyl viologen solution with a pH of 7.4 was prepared to a concentration of 0.5 mmol / L. -1 The concentration of dopamine solution was 0.5 mmol / L. -1 A mixed solution was prepared by placing the substrate electrode ITO (indium tin oxide) electrode into the mixed solution and then using a continuous cyclic voltammetry-driven method to co-assemble methyl viologen and dopamine through redox reaction to obtain a methyl viologen-dopamine polymer enzyme-modified ITO electrode; a substrate electrode CC (carbon cloth) electrode was prepared by placing the substrate electrode CC (carbon cloth) electrode into the mixed solution and then using a continuous cyclic voltammetry-driven method to co-assemble methyl viologen and dopamine through redox reaction to obtain a methyl viologen-dopamine polymer enzyme-modified CC electrode.
[0011] The continuous cyclic voltammetry driving method used has a potential range of -1.0V to 0.6V and a scan rate of 0.1V / s. -1 The number of sedimentary rings is 20.
[0012] A methyl viologen-dopamine polymer enzyme-mimicking electrode obtained by the above method.
[0013] The methyl viologen-dopamine polymer enzyme-mimicking electrode was prepared using differential pulse voltammetry, with a potential range of -1.0V to 0V and a scan rate of 0.1V / s. -1 The electrode is used at concentrations of 0.1-50 mmol / L. -1 The oxidation peak current in glucose PBS solution increases with increasing glucose solution concentration.
[0014] The aforementioned application of the methyl viologen-dopamine polymer-mimicked enzyme catalytic electrode in a glucose fuel cell involves using methyl viologen-dopamine polymer-mimicked enzyme modified ITO as the anode and a methyl viologen-dopamine polymer-mimicked enzyme modified CC electrode as the cathode to assemble and construct a glucose fuel cell. The open-circuit voltage of this glucose fuel cell is 0.683V, and the short-circuit current density is 49.8μA cm⁻¹. -2 The maximum power density is 15.2 μW cm⁻¹ at 0.462 V. -2 .
[0015] The present invention has the following advantages and beneficial effects compared with the prior art:
[0016] (1) The present invention uses a continuous cyclic voltammetry-driven redox co-assembly method to prepare methyl viologen-dopamine polymer electrodes. The preparation method is simple and easy to control the deposition amount and degree of polymerization.
[0017] (2) The electrode prepared by the present invention not only has outstanding glucose oxidase-like activity for glucose oxidation, but also has good electrocatalytic activity for oxygen reduction.
[0018] (3) The glucose fuel cell assembled using the methyl viologen-dopamine polymer enzyme-mimicking catalytic electrode of the present invention as both the anode and cathode catalyst exhibits high open-circuit voltage and power density. The assembled fuel cell does not require precious metal catalysts or enzyme catalysts, and is characterized by simple operation, green environmental protection, safety and high efficiency. Attached Figure Description
[0019] Figure 1 The methyl viologen-dopamine polymer enzyme-mimicking electrode in Example 1 of this invention was prepared by a continuous cyclic voltammetric co-assembly method.
[0020] Figure 2 The methyl viologen-dopamine polymer-based enzyme-mimicking electrode in Example 2 of this invention was used when the concentration of the glucose solution was changed from 0.1 to 50 mmol / L. -1 Differential pulse voltammetry.
[0021] Figure 3 The open-circuit voltage, short-circuit current density, and maximum power density of the glucose fuel cell assembled in Example 3 of this invention, using an ITO electrode modified with methyl viologen-dopamine polymer as the anode and a CC electrode modified with methyl viologen-dopamine polymer as the cathode, were tested. Detailed Implementation
[0022] The present invention will be further described in detail below with reference to embodiments, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods existing in the technical field; unless otherwise specified, the materials and reagents used are commercially available.
[0023] Example 1: Preparation of a methyl viologen-dopamine polymer-mimicking enzyme catalytic electrode
[0024] like Figure 1 As shown, a methyl viologen-dopamine polymer enzyme-mimicking electrode was prepared by the following method:
[0025] (1) Use a concentration of 0.2 mmol / L -1 Prepare a 0.5 mmol / L methyl viologen solution using PBS with a pH of 7.4. -1 And the dopamine concentration was 0.5 mmol / L -1 A mixed solution;
[0026] (2) The ITO electrode was placed in the mixed solution obtained in step (1), and the methyl viologen and dopamine were redox co-assembled using a continuous cyclic voltammetry-driven method to prepare the methyl viologen-dopamine polymer enzyme-modified ITO electrode.
[0027] (3) The CC electrode was placed in the mixed solution obtained in step (1), and the methyl viologen and dopamine were redox co-assembled using a continuous cyclic voltammetry-driven method to prepare the methyl viologen-dopamine polymer enzyme-modified CC electrode.
[0028] Example 2: The methyl viologen-dopamine polymer enzyme-modified ITO electrode of the present invention, when glucose is varied from 0.1 to 50 mmol / L... -1 Differential pulse voltammetry.
[0029] like Figure 2 As shown, the methyl viologen-dopamine polymer enzyme-modified ITO electrode prepared in Example 1 was placed in PBS solution, and differential pulse voltammetry was used. 0.1-50 mmol L of [a specific ingredient / component] was gradually added to the PBS solution. -1The peak current of the electrode increased with the increase of glucose solution concentration, indicating that the prepared methyl viologen-dopamine polymer enzyme-modified ITO electrode has a catalytic effect on glucose.
[0030] Example 3: Using the methyl viologen-dopamine polymer enzyme-modified ITO obtained in Example 1 as the anode and the methyl viologen-dopamine polymer enzyme-modified CC obtained in Example 1 as the cathode, a glucose fuel cell was assembled and constructed. The specific operation steps are as follows:
[0031] like Figure 3 As shown, ITO modified with methyl viologen-dopamine polymer as an enzyme was placed in 1 mmol / L solution as the anode. -1 A glucose fuel cell was constructed by immersing a glucose-containing PBS solution, using a methyl viologen-dopamine polymer-modified CC electrode as the cathode, and placing it in an oxygen-fluidized PBS solution. The anode and cathode were connected via a salt bridge. The open-circuit voltage of this glucose fuel cell was 0.683V, and the short-circuit current density was 49.8μA cm⁻¹. -2 The maximum power density is 15.2 μW cm⁻¹ at 0.462 V. -2 .
[0032] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.
Claims
1. A method for preparing a methyl viologen-dopamine polymer-mimicking enzyme catalytic electrode, characterized in that... Includes the following steps: Using a concentration of 0.2 mmol / L -1 A methyl viologen solution with a pH of 7.4 was prepared to a concentration of 0.5 mmol / L. -1 The concentration of dopamine solution was 0.5 mmol / L. -1 A mixed solution was prepared by placing the substrate electrode ITO into the mixed solution and then using a continuous cyclic voltammetry-driven method to co-assemble methyl viologen and dopamine redox to obtain a methyl viologen-dopamine polymer enzyme-modified ITO electrode. A substrate electrode CC was also placed into the mixed solution and then used a continuous cyclic voltammetry-driven method to co-assemble methyl viologen and dopamine redox to obtain a methyl viologen-dopamine polymer enzyme-modified CC electrode. A glucose fuel cell was constructed by using the methyl viologen-dopamine polymer enzyme-modified ITO as the anode and the methyl viologen-dopamine polymer enzyme-modified CC electrode as the cathode.
2. The method for preparing a methyl viologen-dopamine polymer-based enzyme-mimicking electrode according to claim 1, characterized in that: The continuous cyclic voltammetry driving method used has a potential range of -1.0 V to 0.6 V and a scan rate of 0.1 V / s. -1 The number of sedimentary rings is 20.
3. A methyl viologen-dopamine polymer enzyme-mimicking electrode obtained by the method of any one of claims 1-2.
4. The methyl viologen-dopamine polymer enzyme-mimicking electrode according to claim 3, characterized in that: The methyl viologen-dopamine polymer enzyme-mimicking electrode employs differential pulse voltammetry, with a potential range of -1.0 V to 0 V and a scan rate of 0.1 V / s. -1 The electrode is used at concentrations of 0.1-50 mmol / L. -1 The oxidation peak current in glucose PBS solution increases with increasing glucose solution concentration.
5. The application of the methyl viologen-dopamine polymer enzyme-mimicking electrode according to claim 3 in a glucose fuel cell, characterized in that: The application described uses methyl viologen-dopamine polymer-modified ITO as the anode and methyl viologen-dopamine polymer-modified CC electrode as the cathode to assemble and construct a glucose fuel cell. The open-circuit voltage of this glucose fuel cell is 0.683 V, and the short-circuit current density is 49.8 μA cm⁻¹. -2 The maximum power density is 15.2 μW cm⁻¹ at 0.462 V. -2 .