CN108152348B - Preparation method and application of PDMS-based micro soft Ag/AgCl electrode capable of being used repeatedly - Google Patents
Preparation method and application of PDMS-based micro soft Ag/AgCl electrode capable of being used repeatedly Download PDFInfo
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Abstract
The invention relates to the field of electrochemical electrode preparation, in particular to a preparation method and application of a PDMS-based micro soft Ag/AgCl electrode capable of being used repeatedly. According to the invention, flexible PDMS is used as an electrode substrate material, the surface of the electrode substrate material is subjected to hydrophilic modification, then silver nanowires are uniformly coated on the electrode substrate material, and the electrode substrate material is soaked in NaClO solution and oxidized to prepare the Ag/AgCl electrode. The Ag/AgCl electrode of the invention is used as a reference electrode, which shows good working stability and sensitivity, and the working potential is lower than that of the traditional electrode, and the Ag/AgCl electrode can work for more than 1 hour. The electrode of the invention can be repeatedly used for many times, the material is non-toxic and the biocompatibility is good, and the electrode can be widely applied to a micro-channel system and can be developed and used as a biosensor.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to preparation and application of a reusable PDMS-based micro-fluidic electrode Ag/AgCl electrode.
Background
In recent electrochemical studies, the study of miniature reference electrodes has been of great interest. The Ag/AgCl electrode is one of reference electrodes with the widest application, and has the advantages of stable work, simple preparation process, no potential safety hazard and the like, so the Ag/AgCl electrode has important significance in biological monitoring and microfluidic detection. At present, the miniature Ag/AgCl electrode is prepared mainly by adopting a screen printing technology, PET is used as an electrode substrate, silver ink is used as conductor slurry, and silver paste is printed on the substrate to prepare the electrode. Although the method is simple to operate and can be used for batch industrial production, the surface state of the electrode is difficult to control, and the operation is unstable due to large electrode performance difference among batches. The technology is difficult to design and regulate the size and the shape of the electrode; a large amount of material is wasted. Because the electrode substrate PET is easy to be deformed by heat, and the biocompatibility is poor, the electrode substrate PET can not be used for monitoring at high temperature and in organisms. Then silva[1]The Ag/AgCl electrode for ink-jet printing is researched, and the method has the advantages that the shape of the electrode can be designed and the size can be regulated and controlled automatically, the working stability is excellent, the Ag/AgCl electrode can be printed on various substrates, the cost is saved, and the like. However, the Ag/AgCl layer on the surface of the electrode is easy to fall off after the Ag electrode is oxidized, so that the sustainable stable working time is only within 30 minutes. And Rius-Ruiz[2]The Ag/AgCl reference electrode modified by the carbon nano tube is prepared after 3minStable operation and low sensitivity.
[1]Silva，D.；Miserere，S.；Kubota，T.，Simple On-Plastic/Paper Inkjet-Printed Solid-StateAg/AgCl Pseudoreference Electrode，Anal.Chem.2014，86，10531-10534
[2]F.XavierRius-Ruiz，DiegoBejarano-Nosas，Blondeau，P.，Riu，J.，Disposable Planar Reference Electrode Based on Carbon Nanotubes andPolyacrylate Membrane，Anal.Chem.2011，83，5783–5788.
Disclosure of Invention
The invention aims to prepare a repeatable micro soft Ag/AgCl electrode, and the size and the shape of the electrode can be regulated and controlled by a silica gel photoetching technology. The invention uses PDMS as the base material of the reference electrode for the first time, uses silver nanowires as the working layer of the electrode, and prepares the Ag/AgCl electrode by a chemical oxidation method.
In order to achieve the purpose, the invention adopts the technical scheme that: the method comprises the steps of taking flexible PDMS as an electrode substrate material, soaking the electrode substrate material in a modification solution consisting of 5wt% of Gly and 2wt% of PVA for surface hydrophilic modification, then uniformly coating silver nanowires on the surface of the electrode substrate material, drying for 2 hours at 60 ℃, and soaking in NaClO solution for oxidation to obtain the Ag/AgCl electrode.
The invention also aims to protect the application of the Ag/AgCl electrode, and the three-electrode system is formed by taking a glassy carbon electrode as a working electrode, taking Ag/AgCl as a reference electrode and taking a platinum wire as an auxiliary electrode. The three-electrode system was placed in KCl (10)- 4mol/L) solution.
the invention uses PDMS as the base material of the reference electrode for the first time, which has the advantages of low cost, recycling, good biocompatibility and the like, and the working stability of the electrode using PDMS as the base material is superior to that of PVC and PET.
Drawings
FIG. 1 is a graph of oxidant concentration selection for a silver nanowire electrode;
FIG. 2 is a graph of chronopotentiometric optimized oxidation time;
FIG. 3 is a comparative test chart of Ag/AgCl electrode of the present invention and a conventional commercial electrode;
FIG. 4 is a graph of comparative timing potential curves of long and short silver nanowires and deposited nano silver;
FIG. 5 is PET; PVA; PDM is respectively used as a substrate of the reference electrode to prepare a comparison timing potential curve graph of the Ag/AgCl reference electrode;
FIG. 6 is a graph of Ag/AgCl reference electrode working sustainable time timing potential;
FIG. 7 is a graph of electrode reserve stability test timing potential;
FIG. 8 is a graph of electrode performance test timing potential of a three-electrode system in a KCl supporting electrolyte solution after standing for 24 h;
FIG. 9 is a graph of electrode performance test timing potential after working for 30min and standing for 24h, and replacing supporting electrolyte solution KCl;
FIG. 10 is a graph of electrode performance test timing potential after working for 60min and standing for 24h, replacing supporting electrolyte solution KCl;
FIG. 11 is a graph of electrode performance test timing potential after working for 90min and standing for 24h, replacing supporting electrolyte solution KCl;
FIG. 12 is a graph of electrode performance test timing potential after being left for 24h without replacing the supporting electrolyte solution KCl;
FIG. 13 is a graph of electrode performance test timing potential after working for 30min and standing for 24h without changing the supporting electrolyte solution KCl;
FIG. 14 cyclic voltammogram with nanowires Ag/AgCl as the reference electrode;
FIG. 15 is a schematic of a home-made reference electrode.
Detailed Description
The technical solution of the present invention is described in detail below with reference to the accompanying drawings and examples. The silver nanowires were purchased from Nanjing Xiancheng nanomaterial science and technology Co.
PDMS in the following examples was prepared from 90wt% PDMS mixed with 10 wt% curing agent and cured at 100 ℃ for 2 h.
Example 1 preparation of an Ag/AgCl reference electrode:
1. preparing an electrode substrate mold:
(1) preparing two baking glue machines, adjusting to 65 deg.C and 200 deg.C respectively, cleaning new silicon wafer with nitrogen gas, placing on a hot plate, and heating with 200 deg.C baking glue machine for 5 min. The wafer was then cooled at room temperature.
(2) The center of a silicon wafer is aligned with the center of a turntable of a spin coater, photoresist is dripped into the center of the silicon wafer, bubbles cannot be generated in the dripping process, the photoresist is slowly spun for 20s at a rotating speed of 500r/min, then the silicon wafer is placed on a 65 ℃ photoresist baking machine to be heated for 5min, the silicon wafer is heated for 20min at 95 ℃, and the silicon wafer is cooled for 10min at room temperature after the heating is finished.
(3) Placing the silicon wafer in a mask plate, exposing under an ultraviolet exposure machine with wavelength of 280nm, placing the exposed silicon wafer on a hot plate, heating for 5min with a 65 ℃ glue baking machine, and then heating for 11min on a 95 ℃ glue baking machine. Finally cooling to room temperature.
(4) Taking the silicon wafer off the hot plate, placing the silicon wafer in a glass culture dish, adding a developing solution, and slightly shaking the silicon wafer until the pattern is clear and visible. And washing away the redundant developing solution by using acetone and deionized water, and airing at room temperature.
2. Preparing an electrode working layer chip:
mixing 90wt% of PDMS and 10 wt% of silane coupling agent, pouring the mixture into an electrode substrate mould, and curing for 2h at 100 ℃ to obtain the flexible PDMS. And then hydrophilic modification is carried out on the flexible PDMS, the modification solution consists of 5wt% (Gly) and 2wt% (PVA), the flexible PDMS is soaked in the modification solution for 20min, then the flexible PDMS is taken out and dried for 2h at 60 ℃, the operation is repeated for three times, finally, the silver nanowires are uniformly coated, electrode oxidation treatment is carried out after the flexible PDMS is dried for 2h at 60 ℃, the flexible PDMS is soaked in NaClO (20mg/mol), and finally, the flexible PDMS is washed by deionized water and dried for 2h at 60 ℃ to obtain the Ag/AgCl reference electrode.
Preparing an Ag/AgCl electrode PDMS hollow shell and a PDMS film:
the PDMS hollow shell of the electrode is prepared by adopting the same preparation method as the flexible PDMS, and the shell is of an internal hollow structure and is used for storing supporting electrolyte kcl. Then preparing glue to bond the PDMS hollow shell with the Ag/AgCl electrode, wherein the glue can be prepared by mixing 90wt% of PDMS and 10 wt% of curing agent (such as silane coupling agent).
The PDMS membrane is an encapsulation device of the uppermost layer of the electrode, the preparation operation is the same as that of the PDMS hollow shell, and a puncher is needed to punch holes at the end of preparation. The electrode is schematically shown in FIG. 15.
Example 2
The Ag/AgCl electrode prepared in example 1 was used as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum wire as an auxiliary electrode to form a three-electrode system.
Pretreating a glassy carbon electrode: polishing and activating glassy carbon electrode, and using Al with different grain sizes 203And (3) placing the powder on the deer skin from big to small, and dripping less deionized water on the deer skin to polish the electrode.
The three-electrode system of this example was used for electrode testing:
the three-electrode system is placed in PBS (10x) buffer solution, under the three-electrode system, a chronopotentiometry method is adopted, the cathodic current is set to be 2 muA, the anodic current is set to be 2 muA, the cathodic time is set to be 2s, the anodic time is set to be 600s, the initial polarity is the anode, the data storage interval is 0.01s, the number of segments is 2, and the electrode polarity switching mode is set to be time. The chronopotentiometric curve is shown in FIG. 3.
As shown in FIG. 3, the comparative test chart of the electrode operation (a chronopotentiometry; b impedance test) shows that the Ag/AgCl nanowire electrode prepared in example 1 can be used for about 20s from the start of the test to the stable operation of the electrode by comparing with the conventional commercial electrode, and the commercial electrode can be stably operated after the time of the chronopotentiometry, the Ag/AgCl nanowire electrode has the electrode potential reduced by the nanostructure and is lower than the conventional commercial reference electrode by about 26.3%, the measurement application range and the accuracy of the reference electrode are widened, the comprehensive impedance test shows that the electron transfer capacity of the Ag/AgCl nanowire electrode in a low frequency region is higher than that of the conventional commercial electrode, and the Delta E of the Ag/AgCl nanowire electrode is less than 3mv after 340 s.
Example 3
The three-electrode system consists of a glassy carbon electrode as a working electrode, the nanowire Ag/AgCl prepared in example 1 as a reference electrode, and a platinum wire as an auxiliary electrode.
Pretreating a glassy carbon electrode: polishing and activating glassy carbon electrode, and using Al with different grain sizes 203And (3) placing the powder on the deer skin from big to small, and dripping less deionized water on the deer skin to polish the electrode.
The three-electrode system of this example was used for electrode testing:
the three electrode system places the electrode in potassium ferricyanide (10)-6mol/L) solution, under a three-electrode system, adopting cyclic voltammetry, setting the scanning potential range to be-0.8 to 1.0v, the scanning speed to be 0.1v/s, the number of turns to be 1 turn, and showing the cyclic voltammetry curve in figure 15.
The technological parameters for preparing the reference electrode Ag/AgCl are optimized, and the test results are as follows.
FIG. 1 is a diagram of the selection of oxidant concentration for nano Ag wire electrode. As shown in FIG. 1, a shows the structure of the nano silver wire on the surface layer of the unoxidized Ag electrode, b shows the structure of Ag/AgCl after soaking in an oxidant NaClO (40mg/mol) for 60s, and c shows the structure of Ag/AgCl after soaking in an oxidant NaClO (20mg/mol) for 60 s. And d, detecting the atomic energy spectrum of the surface layer of the electrode, and comparing the atomic energy spectrums of the surface layers of the electrode before and after oxidation to show that AgCl is generated after oxidation. And e and f are respectively an impedance analysis and a chronopotentiometry of the oxidant with different concentrations. In conclusion, the analysis can determine that the concentration of the oxidant NaClO is 20mg/mol, and the working performance of the Ag/AgCl reference electrode is optimal.
FIG. 2 is a diagram of oxygen optimization by chronopotentiometryAnd (5) forming a time chart. Place the three-electrode system in KCl (10)-4mol/L) solution, adopting a chronopotentiometry, setting the cathodic current to be 2 muA, the anodic current to be 2 muA, the cathodic time to be 2s, the anodic time to be 600s, the initial polarity to be the anode, the data storage interval to be 0.01s, the number of segments to be 2, and the electrode polarity switching mode to be time. Finally, the optimal oxidation time of the reference electrode Ag/AgCl is determined to be 60 s.
FIG. 4 shows the comparison between long and short silver nanowires and deposited nano silver, and the detection is performed by a chronopotentiometry method, which finally proves that the short silver nanowire (60 μm in length and 90nm in diameter) has the best electrode performance. The electrode potential of the deposited nano silver particles is highest but the working stability is poor, which shows that the silver nano particles are unevenly distributed on the nano silver wire, and the conduction electrons are unstable. The working potential of the short nano silver wire electrode is higher than that of the long nano silver wire electrode, and the working stability is good, so the short silver nanowire is the best material for the electrode working layer.
FIG. 5 shows the comparison of Ag/AgCl reference electrodes made of PET, PVA and PDMS as the reference electrode substrate, respectively, and the detection is performed by a time potential method, which finally proves that the substrate electrode performance of PDMS as the reference electrode is the best.
FIG. 6 shows a time potential method for investigating the service life of an Ag/AgCl reference electrode, in which the electrode prepared in example 1 was used as a reference electrode and PBS buffer was used as an electrode working environment. The homemade Ag/AgCl reference electrode is proved to be capable of stably working for more than 1 h.
Fig. 7 shows an electrode storage stability test, which shows that the potential is obviously reduced after the electrode is stabilized after the electrode is continuously placed for 15 days, and finally proves that the self-made electrode is easily oxidized, so that the potential is reduced, the performance of the electrode is unstable, and the electrode needs to be stored in nitrogen.
A three-electrode system is formed by taking a glassy carbon electrode as a working electrode, the nano-wire Ag/AgCl prepared in example 1 as a reference electrode and a platinum wire as an auxiliary electrode, and after the three-electrode system is placed for 24 hours, a supporting electrolyte solution KCl (10) is replaced-4and testing the performance of the mol/L electrode by adopting a time potential method, wherein the testing time is 10min each time, the testing is carried out for three times, the testing results are shown in figure 8, the repeatability of the electrode is excellent, and △ is obtained after 10min of working and 20min of workingE<5mv, work 20min later and work 30min later delta E<6mv。
After the electrode works for 30min and is placed for 24h, the performance test of the electrode of the supporting electrolyte solution is replaced, and the test is carried out by adopting a time potential method, wherein the time length of each test is 10min, and the test is carried out for three times. The test results are shown in fig. 9, where a drop of about 2.4% in potential occurred after 20min of operation.
After the electrode works for 60min and is placed for 24h, the performance test of the electrode which supports the electrolyte solution is replaced, and the test is carried out by adopting a timing potential method, wherein the test time is 10min each time, and the test is carried out for three times. The test results are shown in fig. 10, and it can be seen that the chronopotentiometric curves obtained from the three tests are stable, so that the electrode can be considered to be still stably operated.
FIG. 11 shows the performance test of the electrode with replacement supporting electrolyte solution after 90min of operation. The electrode potential obviously fluctuates by adopting a timing potential method for testing, so that the electrode is considered to be invalid.
FIG. 12 shows that after being left for 24h, the electrode performance test of the supporting electrolyte solution is not changed, and the test is carried out by adopting a time potential method, wherein the time length of each test is 10min, and the test is carried out for three times. It can be seen that the chronopotentiometric curves obtained from the three tests are stable, so that the electrode can be considered to be still working stably.
FIG. 13 shows that after working for 30min, the sample is left for 24h and tested by a chronopotentiometry method without changing the performance of the supporting electrolyte solution electrode. The electrode was considered to be ineffective because the electrode potential significantly fluctuated (i.e., the chronopotentiometric curve fluctuated in a polygonal line).
As shown in FIG. 14, the nanowire Ag/AgCl reference electrode of the invention can work normally in a system where oxidation and reduction occur.
Claims (3)
1. A preparation method of a PDMS-based micro soft Ag/AgCl electrode capable of being used repeatedly is characterized in that flexible PDMS is used as an electrode substrate material, the electrode substrate material is soaked in a modification liquid composed of 5wt% of Gly and 2wt% of PVA for surface hydrophilic modification, silver nanowires are uniformly coated on the surface of the electrode substrate material, and after the electrode substrate material is dried at 60 ℃ for 2 hours, the electrode substrate material is soaked in a NaClO solution with the concentration of 20mg/mL for oxidation to prepare an Ag/AgCl electrode working layer chip;
preparing a PDMS hollow shell of the electrode by adopting the same preparation method as flexible PDMS, wherein the shell is of an internal hollow structure and is used for storing supporting electrolyte kcl, and then preparing glue to bond the PDMS hollow shell with an Ag/AgCl electrode working layer, wherein the glue is prepared by mixing 90wt% of PDMS and 10 wt% of silane coupling agent;
the PDMS film is an encapsulation device of the uppermost layer of the electrode, the preparation operation is the same as that of the PDMS hollow shell, and a puncher is needed to punch holes at the position of the PDMS film corresponding to the Ag/AgCl electrode at the end of preparation;
the flexible PDMS is prepared by mixing 90wt% of PDMS and 10 wt% of silane coupling agent, pouring the mixture into an electrode substrate mould, and curing for 2h at 100 ℃;
the method for hydrophilic modification of the surface comprises the following steps: soaking the electrode substrate material in a modification liquid consisting of 5wt% of Gly and 2wt% of PVA for 20min, taking out, drying at 60 ℃ for 2h, and repeatedly operating for 2-3 times.
2. The method of claim 1, wherein the electrode substrate mold is prepared using a silicon wafer lithography gel.
3. Use of an Ag/AgCl electrode prepared according to the method of claim 1, wherein the Ag/AgCl electrode is used as a reference electrode, the glassy carbon electrode is used as a working electrode, and the platinum wire is used as an auxiliary electrode, to form a three-electrode system.
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| CN112285181A (en) * | 2020-10-23 | 2021-01-29 | 徐州工业职业技术学院 | Preparation method of enzyme sensor for realizing hydrogen peroxide detection |
| CN112967832B (en) * | 2021-02-01 | 2023-02-28 | 天津理工大学 | Flexible comb-shaped semi-dry electrode and preparation method thereof |
| CN113647952A (en) * | 2021-08-18 | 2021-11-16 | 北京航空航天大学 | Flexible dry electrode made of silver/silver chloride nanowires and preparation method thereof |
| CN116246836A (en) * | 2021-12-07 | 2023-06-09 | 深圳先进技术研究院 | Elastic dry electrode and preparation method and application thereof |
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| CN106198660A (en) * | 2016-07-15 | 2016-12-07 | 大连大学 | A kind of method depositing nanometer silver in micro-fluidic duct |
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