CN114583188A - Method for constructing neutral glucose fuel cell electrode - Google Patents
Method for constructing neutral glucose fuel cell electrode Download PDFInfo
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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 65
- 239000008103 glucose Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract description 9
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract 10
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Abstract
The invention belongs to the technical field of electrochemical detection, and discloses a method for constructing a neutral glucose fuel cell electrode. The invention utilizes the flexibility of PDMS and the high specific surface area, high conductivity and high catalytic activity of silver nanowires and palladium-gold alloy, and the prepared electrode has good catalytic effect on glucose, high sensitivity and good selectivity, and has stable performance and low detection limit, and the excellent performances enable the Pd-Au-AgNWs electrode to have wide application prospect in the field of electrochemical sensors.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection, and particularly relates to a method for constructing a neutral glucose fuel cell electrode.
Background
As a conversion device capable of directly converting chemical energy of fuel into electric energy through electrochemical reaction, a fuel cell has advantages of high energy conversion efficiency and the like, which are widely researched and applied by people, because the power generation is not limited by carnot cycle. Glucose is the most widely distributed and abundant monosaccharide in nature, and is also one of important nutrients and main heat sources in organisms, however, the chemical property of glucose is very stable and is difficult to be oxidized electrochemically, so that directly using glucose as a fuel cell becomes a great challenge in the current research of glucose fuel cells. Glucose oxidase is widely used in enzymatic fuel cells because of its selectivity for glucose, but glucose oxidase is easily affected by temperature, pH, toxic chemicals and humidity, thus limiting the durability, stability and hindering further development of the cells, and in order to overcome these disadvantages, it is necessary to research glucose fuel cells that do not use enzymes.
In recent years, non-enzymatic nanoelectrodes have been attracting attention due to their low cost, high stability and high catalytic activity. The electrode or modified material on the electrode acts as an electrocatalyst instead of the enzyme, and the high specific surface area of the electrode material facilitates ion and mass diffusion, thereby providing more active sites. Meanwhile, the low resistance and the high conductivity of the nano material are beneficial to promoting the electron transfer and the catalytic process on the surface of the electrode, and the nano material is used as a catalyst, so that the problems of specificity, stability and the like of the enzyme are solved to a great extent.
Existing glucose fuel cell electrodes are mainly alkaline because glucose activity is low under neutral conditions, and reports on the glucose fuel cell electrodes are few. LargeaudF et al explain why the electrode readily catalyzes glucose under alkaline conditions using Density Functional Theory (DFT) calculations. In addition, since many glucose sensors employ non-noble metals, metal oxides, and the like, and such materials exhibit poor stability in neutral and acidic environments, research and study on glucose fuel cells under neutral and acidic conditions have been rare.
The inventors of the present patent application have detected or catalyzed PDMS by depositing a single metal after coating AgNWs, but neither the previously applied patents nor the electrodes prepared in the published papers can be applied to neutral fuel cells. This is because a large amount of complex ions exist under neutral conditions, and metals such as Ag and Au have poor stability under neutral conditions, resulting in low durability. In glucose neutral fuel cells, PB or PBs is often used as a supporting electrolyte solution. Guohui Chang task group[1]The nano-silver modified polyaniline nano-fiber is prepared by taking a glassy carbon electrode as a substrate, using a supporting electrolyte solution as a 0.2M PBS solution, and using a cyclic voltammetry catalytic potential range of-1.0V-0.2V. The invention adopts silver nano-wires as a substrate, has higher specific surface area compared with nano-silver, is more beneficial to the transmission of electrons, adopts an electrochemical deposition method, prepares the Pd-Au-AgNWs electrode by uniform deposition, uses a supporting electrolyte solution of 0.1M PBS solution, and uses a cyclic voltammetry catalytic potential range of-0.7V-1V. Yu Bai subject group[2]Preparing Pt-Pb nanowire array electrode by electrochemical deposition, wherein Pd is deposited by adopting a chronoamperometry, and Pb (NO) is used as supporting solution3)2The catalytic potential range of the cyclic voltammetry is-0.6V-1V. The method adopts cyclic voltammetry to deposit Pd, the deposition potential is 0.25-0.4V, the sweep rate is 25mV/s, and the catalytic potential range of the cyclic voltammetry is-0.7V-1V. Xing Qiao topic group[3]The alloy-structured Au-Co bimetallic nanoparticle modified graphene oxide is synthesized by a one-step in-situ chemical reduction method, and the adopted electrochemical method is an electrochemical luminescence method. The invention adopts an electrochemical deposition method, controls the nano-morphology by controlling the deposition method and the deposition conditions, and prepares the nano-particles by uniform depositionThe Pd-Au-AgNWs electrode is prepared, and the adopted electrochemical method is cyclic voltammetry. YIpen Sun task group[4]The Pt-Pb alloy electrode is prepared by adopting a supporting electrolyte solution of 0.1M PB solution, a catalytic potential of-0.4V-0.8V and a sweep rate of 5mV/s through cyclic voltammetry. The invention prepares a dendritic nano structure by an electrochemical deposition method, prepares a Pd-Au-AgNWs electrode by uniform deposition, uses a supporting electrolyte solution as a 0.1M PBS solution, adopts a cyclic voltammetry catalytic potential range of-0.7V-1V, and has a sweep rate of 50 mV/s. The nano-morphology of the electrodes is mostly one-dimensional nano-wires, nano-particles, nano-chains and the like, and the nano-electrode is nano-dendritic, has higher electrochemical active surface area and higher catalytic efficiency. Honghui Shu topic group[5]Gold nano-structure is directly electrodeposited on a glassy carbon electrode, and glucose is catalyzed by adopting a linear scanning voltammetry method at a scanning speed of 100 mv/s. The invention prepares a dendritic nano structure by an electrochemical deposition method, prepares a Pd-Au-AgNWs electrode by uniform deposition, adopts a cyclic voltammetry catalytic potential range of-0.7V-1V, and has a sweep rate of 50 mV/s. Simultaneous Honghui Shu topic group[6]Three-dimensional gold nanoparticles are prepared on the graphene by adopting electrochemical deposition, the catalytic potential range is 0.4V-1.5V by adopting cyclic voltammetry, and the sweep rate is 5 mV/s. The invention prepares a dendritic nano structure by an electrochemical deposition method, prepares a Pd-Au-AgNWs electrode by uniform deposition, adopts a cyclic voltammetry catalytic potential range of-0.7V-1V, and has a sweep rate of 50 mV/s. Although the three-dimensional dendritic or spherical nano structure is prepared by the electrochemical method, compared with the invention, the electrode has the advantages of low catalytic current, lack of palladium protection, poor stability and low reproducibility. We have also previously patented gold deposition on silver nanowires, but the amount of gold previously deposited was relatively small, so that the gold deposited had only a nanoparticle structure, no gold-branch structure, and no palladium element. Therefore, the nano silver-gold material in the previous patent does not have the property of catalyzing glucose in a neutral solution.
Moreover, the oxidation performance of the conventional electrode on glucose is easily influenced by pH, and the performance and the service life of the electrocatalyst are limited under the conditions of high alkalinity and high acidity. Therefore, it is particularly important to construct a neutral glucose fuel cell electrode.
Disclosure of Invention
Aiming at the defects, the invention provides a method for constructing a neutral glucose fuel cell electrode, which comprises the steps of taking PDMS (polydimethylsiloxane) as a substrate, uniformly coating silver nanowires, depositing gold by a chronoamperometry method and depositing palladium by a cyclic voltammetry method, thus preparing a palladium-gold alloy nano electrode, researching the influence of the palladium-gold alloy nano electrode on the glucose oxidation performance under the neutral condition, and having higher catalytic activity on the glucose oxidation and low manufacturing cost.
The above purpose of the invention is realized by the following technical scheme:
a method for constructing a neutral glucose fuel cell electrode comprises the steps that an electrode substrate is PDMS, the lower portion is AgNWs, Pd and Au form a unique pine-shaped nano structure on a nanowire, a Pd-Au-AgNWs electrode which is constructed is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire is used as an auxiliary electrode to form a three-electrode system, the three-electrode system is placed in a glucose solution and a supporting electrolyte, the set potential is-0.7-1.0V, and the scanning rate is recorded as 50mV s-1And analyzing the control process of the electrode electro-catalytic oxidation of the glucose solution by using a standard curve method.
Further, the substrate PDMS is subjected to surface hydrophilic layer modification.
Further, the specific steps of the substrate PDMS for surface hydrophilic layer modification are as follows:
(1) preparing a mixed solution of 3 mass percent of polyvinyl alcohol PVA and 5 mass percent of glycerol Gly;
(2) soaking the PDMS substrate in a mixed solution of PVA and Gly for 20min, removing the redundant liquid on the surface, and then drying in a vacuum oven at 60 ℃ for 2 h;
(3) repeating the step (2) twice;
(4) and (3) putting the PDMS substrate into a vacuum oven at 100 ℃ for drying for 2h to obtain the PDMS substrate with the surface hydrophilic modification layer.
Further, the supporting electrolyte is 0.1M PBS solution.
Further, the Pd-Au-AgNWs electrode comprises: AgNWs are uniformly coated on the surface-modified PDMS to form a conductive coating, and the nano palladium-gold particles are electrochemical deposition layers and are deposited on the AgNWs.
Further, the preparation method of the Pd-Au-AgNWs electrode comprises the following steps:
(1) 100. mu.L of 3mg mL-1Uniformly coating the AgNWs solution on the surface of the modified PDMS, and preparing the silver nanowire flexible electrode after the AgNWs is dried;
(2) adopting a three-electrode system, taking PDMS with AgNWs coating as a working electrode, an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode, and putting 0.5mol/L H2SO4And 2mg/mL of KAuCl4Carrying out constant potential deposition on the nano gold particles in the mixed solution, wherein the deposition voltage is-0.5V, the deposition time is 1500s, after the deposition is finished, slightly washing with ultrapure water, and drying at room temperature to prepare the Au-AgNWs electrode;
(3) a three-electrode system is adopted, an Au-AgNWs electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode system is placed in a buffer solution of acetic acid-sodium acetate with pH of 4 and 8mmol/L PdCl2In the solution, adopting cyclic voltammetry to deposit nano palladium, and setting electrodeposition parameters of an electrochemical workstation: and the potential is 0.25-0.4V, the sweeping speed is 25mV/s, and the Pd-Au-AgNWs electrode is prepared by washing with ultrapure water and drying at room temperature after deposition.
According to the invention, flexible PDMS is used as a substrate, AgNWs is uniformly coated after hydrophilic modification, and a dendritic nano Pd-Au alloy electrode is deposited by an electrochemical deposition method. The dendritic nano structure remarkably increases the specific surface area of the catalyst, provides more active sites for the catalysis of glucose and contributes to more clearly understanding the mechanism of glucose oxidation.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention develops a neutral glucose fuel cell electrode, combines the advantages of silver nanowires, has a high specific surface area, can enlarge the contact area of the electrode to glucose, and increases the sensitivity by forming a unique pine-branch-shaped nano structure by deposited metal and uniformly distributing the metal. When glucose is used as a reference solution, the Pd-Au-AgNWs electrode has high catalytic performance and high selectivity, is simple in preparation method, low in cost and convenient to operate, and is not easily influenced by external factors such as environment.
(2) The invention utilizes the flexibility of PDMS and the high specific surface area, high conductivity and high catalytic activity of silver nanowires and palladium-gold alloy, and the prepared electrode has good catalytic effect on glucose, high sensitivity and good selectivity, and has stable performance and low detection limit, and the excellent performances enable the Pd-Au-AgNWs electrode to have wide application prospect in the field of electrochemical sensors.
(3) The electrodes of the invention can be used in any environment, including acidic, basic, and neutral solutions; compared with a Pd-AuNWs electrode and a Pd-AgNWs electrode, the invention has more outstanding advantages that the Pd-Au-AgNWs electrode is not simply superposed on the microstructure compared with the Pd-AuNWs electrode and the Pd-AgNWs electrode, the Pd-Au-AgNWs electrode has larger specific surface area due to the mutual synergistic effect of metal and metal, and the microstructure is more uniformly distributed, so that the electrochemical activity of the Pd-AuNWs electrode is higher.
The invention constructs a novel Pd-Au-AgNWs multi-metal composite nanowire flexible electrode, the gold and palladium elements have good stability, and the alloy combined by gold and palladium still has good catalytic performance under a neutral condition. The Pd electronic structure can be adjusted by the alloy formed by the transition metal Pd and Au, the d-band center of the Pd is obviously reduced, the adsorption of oxygen is weakened, and the activity and the anti-poisoning capability of the electrode are improved.
The electrode substrate of the battery constructed by the invention is PDMS, the bottom is a nanowire, and Pd and Au form a unique dendritic nanostructure on the nanowire. The novel nano-structure battery motor has large specific surface area and high electron transmission rate. Electrons can enter from a special Pd-Au pine branch-shaped structure and are transmitted through the lower AgNWs, so that the high-stability Pd-Au catalyst has high stability and catalytic current.
The method comprises the steps of taking a constructed Pd-Au-AgNWs electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum wire electrode as a counter electrode to form a three-electrode system, placing the three-electrode system in a glucose solution and a supporting electrolyte, setting the potential to be-0.7-1.0V, recording a cyclic voltammetry curve of glucose, and analyzing the control process of the electrode in the electrocatalytic oxidation of the glucose solution by using a standard curve method.
According to the invention, through contrast deposition of various metals such as Pd, Hg, Pb and the like, the unique deposition method and deposition conditions are found, the Pd can form a compact film on the Au-AgNWs through electrochemical deposition of the Pd, the Au and the Ag can be effectively protected under the protection of the Pd, the stability of the electrode is greatly improved, and the electrode can be used for multiple times under a neutral condition.
Drawings
FIG. 1 is a surface topography diagram of a Pd-Au-AgNWs-based electrode;
FIG. 2 is a surface topography of Pd-AgNWs based electrode;
FIG. 3 is a surface topography of Pd-AuNWs based electrodes;
FIG. 4 is a graph comparing cyclic voltammograms of a glucose solution and a blank PBS solution;
FIG. 5 is a comparison of electrochemical activity of Pd-Au-AgNWs, Pd-AgNWs and Pd-AuNWs electrodes;
FIG. 6 is a plot of cyclic voltammograms of different concentrations of glucose solution in 0.1M PBS solution;
FIG. 7 is a standard curve of different concentrations of glucose in 0.1M PBS solution;
FIG. 8 is a graph showing the stability of Pd-Au-AgNWs electrode.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the specific embodiments, but the present invention is not limited to the embodiments in any way. In the examples, unless otherwise specified, the experimental methods are all conventional methods; unless otherwise indicated, the experimental reagents and materials were commercially available.
The preparation method of the Pd-Au-AgNWs electrode in the following embodiment comprises the following steps:
and 1, modifying the hydrophilic layer on the surface of PDMS.
The method comprises the following specific steps:
(1) preparing a mixed solution of 3 percent (w percent) of polyvinyl alcohol PVA and 5 percent (w percent) of glycerol Gly;
(2) soaking the PDMS substrate in a mixed solution of PVA and Gly for 20min, removing the redundant liquid on the surface, and then drying in a vacuum oven at 60 ℃ for 2 h;
(3) repeating the step (2) twice;
(4) and (3) putting the PDMS substrate into a vacuum oven at 100 ℃ for drying for 2h to obtain the PDMS substrate with the surface hydrophilic modification layer.
2. And (4) preparing an electrode.
The method comprises the following specific steps:
(1) 100. mu.L of 3mg mL-1And uniformly coating the AgNWs solution on the surface of the modified PDMS, and after the AgNWs is dried, preparing the silver nanowire flexible electrode.
(2) Adopting a three-electrode system, taking PDMS with AgNWs coating as a working electrode, an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode, and putting 0.5mol/L H2SO4And 2mg/mL of KAuCl4The mixed solution is used for constant potential deposition of the nano gold particles. The deposition voltage was-0.5V and the deposition time was 1500 s. And after deposition, slightly washing with ultrapure water, and drying at room temperature to prepare the Au-AgNWs electrode.
(3) A three-electrode system is adopted, an Au-AgNWs electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode system is placed in a buffer solution of acetic acid-sodium acetate with pH of 4 and 8mmol/L PdCl2In the solution, the nano palladium is deposited by adopting cyclic voltammetry. Setting electrodeposition parameters of an electrochemical workstation: the potential is 0.25-0.4V, and the sweep rate is 25 mV/s. After deposition, washing with ultrapure water, and drying at room temperature to prepare the Pd-Au-AgNWs electrode.
The surface topography based on the Pd-Au-AgNWs electrode is shown in figure 1: the nano particles on the electrode are uniform in size and distribution, obvious dendritic shapes are formed, the electrocatalytic performance is particularly outstanding, and the stability is good. As shown in fig. 2 and 3, the Pd-Au-AgNWs electrode is not a simple metal composition stack, but rather an intermetallic interaction leads to a larger specific surface area on the microstructure compared to the Pd-AuNWs electrode and the Pd-AgNWs electrode, and the microstructure appears to be more uniformly distributed, so that the electrochemical activity thereof is higher.
Example 1 comparison of Cyclic voltammograms of glucose solution and blank PBS solution
Firstly, placing a three-electrode system in PBS (phosphate buffer solution) with the pH of 7.4 and the concentration of 0.1M, scanning within a potential range of-0.7V to 1.0V by using a cyclic voltammetry method, and recording a cyclic voltammetry curve of a blank solution; then, the three-electrode system was placed in a 30mM glucose test solution containing 0.1M PBS at pH 7.4 as a supporting electrolyte, and scanned over a potential range of-0.7V to 1.0V by cyclic voltammetry to record a cyclic voltammetry curve of glucose.
The results are shown in FIG. 4: the Pd-Au-PDMS electrode was tested for catalytic effect at 30mM glucose at a scan speed of 50m V/s. From the figure, it can be seen that the catalytic current of the Pd-Au-AgNWs electrode to glucose is 11900 mu A/cm2And/mol. The Pd-Au-AgNWs electrode can be used for preparing the fuel, and the fuel is capable of efficiently converting the biological energy into the electric energy.
Example 2
In 0.1M PBS solution, the Pd-Au-AgNWs electrode, the Pd-AgNWs electrode and the Pd-AuNWs electrode respectively carry out cyclic voltammetry response in glucose solution with the concentration of 30 mM.
The three-electrode system was sequentially placed in glucose solutions to be tested of different concentrations containing 0.1M PBS solution with pH 7.4 as supporting electrolyte, the current curve of 30mM glucose was measured at a sweep rate of 50mV/s, and scanning was performed in a potential range of-0.7V to 1.0V using cyclic voltammetry. And recording the cyclic voltammetry curves of the Pd-Au-AgNWs electrode, the Pd-AgNWs electrode and the Pd-AuNWs electrode of glucose with the same concentration and the same scanning speed.
The results are shown in FIG. 5: as can be seen from the figure, the Pd-Au-AgNWs electrode has the highest electrochemical activity in the glucose solution. Compared with a Pd-AgNWs electrode and a Pd-AuNWs electrode, the peak current density of the Pd-Au-AgNWs electrode is greatly improved, and the side surface can prove that the three metals of Pd, Au and Ag are not simply superposed, but the efficiency is greatly improved due to the synergistic effect of the three metals.
Example 3
In 0.1M PBS solution, the Pd-Au-AgNWs electrode is used for carrying out cyclic voltammetry response on glucose solutions with different concentrations.
The three-electrode system was placed in glucose test solutions of different concentrations containing 0.1M PBS solution at pH 7.4 as a supporting electrolyte, and current curves of 10mM, 20mM, 30mM, 40mM, 50mM, 60mM, 70mM, 80mM, 90mM, and 100mM glucose were measured at a sweep rate of 50mV/s, and scanned in a potential range of-0.7V to 1.0V by cyclic voltammetry. Cyclic voltammograms of glucose were recorded at different concentrations and sweep rates.
The results are shown in fig. 6 and 7: as can be seen from the graph, as the concentration is increased continuously, the oxidation current of the nano electrode in the glucose solution is increased continuously, the oxidation peak is increased continuously, and a good linear response for catalyzing glucose is presented. Thus, the redox reaction of glucose is diffusion controlled. There is a good linear relationship between the two in the range of 10-100 mM.
EXAMPLE 4 determination of electrode stability
First, the three-electrode system was placed in a 30mM glucose test solution containing a PBS solution having a pH of 7.4 and a concentration of 0.1M as a supporting electrolyte, and cyclic voltammetry was used to record cyclic voltammetry curves of glucose from the first week to the fourth week at a potential of-0.7V to 1.0V.
The results are shown in FIG. 8: the glucose with the same concentration is catalyzed from the first week to the fourth week, the obtained cyclic voltammetry curves are basically overlapped, and the glucose oxidation peak current RSD is 2.2%, so that the electrode has strong long-term stability and stable structure, and can be well applied to a neutral glucose fuel cell.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A method for constructing a neutral glucose fuel cell electrode is characterized in that an electrode substrate is PDMS, the lower part is AgNWs, Pd and Au form a pine-branch-shaped nano structure on a nanowire, a Pd-Au-AgNWs electrode which is constructed is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum wire is used as an auxiliary electrode to form a three-electrode system, the three-electrode system is placed in a glucose solution and a supporting electrolyte, and the set potential is-0.7-1.0V.
2. The method of claim 1, wherein the substrate PDMS is surface-modified with a hydrophilic layer.
3. The method for constructing a neutral glucose fuel cell electrode according to claim 2, wherein the step of modifying the surface hydrophilic layer of the substrate PDMS is as follows:
(1) preparing a mixed solution of polyvinyl alcohol PVA with the mass fraction of 3% and glycerol Gly with the mass fraction of 5%;
(2) soaking the PDMS substrate in a mixed solution of PVA and Gly for 20min, removing the redundant liquid on the surface, and then drying in a vacuum oven at 60 ℃ for 2 h;
(3) repeating the step (2) twice;
(4) and (3) putting the PDMS substrate into a vacuum oven at 100 ℃ for drying for 2h to obtain the PDMS substrate with the surface hydrophilic modification layer.
4. The method of claim 1, wherein the supporting electrolyte is 0.1M PBS solution.
5. The method of claim 1, wherein the Pd-Au-AgNWs electrode comprises: AgNWs are uniformly coated on the surface-modified PDMS to form a conductive coating, and the nano palladium-gold particles are electrochemical deposition layers and are deposited on the AgNWs.
6. The method of claim 1, wherein the Pd-Au-AgNWs electrode is prepared by:
(1) 100. mu.L of 3mg mL-1Uniformly coating the AgNWs solution on the surface of the modified PDMS, and preparing the silver nanowire flexible electrode after the AgNWs is dried;
(2) adopting a three-electrode system, taking PDMS with AgNWs coating as a working electrode, an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode, and putting 0.5mol/L H2SO4And 2mg/mL of KAuCl4Carrying out constant potential deposition on the nano gold particles in the mixed solution, wherein the deposition voltage is-0.5V, the deposition time is 1500s, after the deposition is finished, slightly washing with ultrapure water, and drying at room temperature to prepare the Au-AgNWs electrode;
(3) a three-electrode system is adopted, an Au-AgNWs electrode is used as a working electrode, a platinum wire electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, and the three-electrode system is placed in a buffer solution of acetic acid-sodium acetate with pH of 4 and 8mmol/L PdCl2In the solution, adopting cyclic voltammetry to deposit nano palladium, and setting electrodeposition parameters of an electrochemical workstation: and the potential is 0.25-0.4V, the sweeping speed is 25mV/s, and the Pd-Au-AgNWs electrode is prepared by washing with ultrapure water and drying at room temperature after deposition.
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