CN116381011A - Novel conductive polymer modified 3D printing electrode and preparation method and application thereof - Google Patents
Novel conductive polymer modified 3D printing electrode and preparation method and application thereof Download PDFInfo
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
Abstract
The invention relates to a novel conductive polymer modified 3D printing electrode, and a preparation method and application thereof, and belongs to the technical field of preparation of 3D printing electrodes. The preparation method is mainly characterized in that SMS solution (beta-cyclodextrin (beta-CD) and citric acid are formed by ultrasonic dispersion in water), polymer solution (polyvinyl alcohol (PVA) aqueous solution is used as a polymer network and glutaraldehyde (50% GA) is used as a cross-linking agent) and aqueous solution of poly (3, 4-dioxyethyl thiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) are stirred to form SACP precursor solution, and the SACP precursor solution is dropwise added on the surface of a gold-modified 3D printing electrode (Au@3DE) through a drop casting method to form a novel conductive polymer-modified 3D printing electrode.
Description
Technical Field
The invention belongs to the technical field of preparation of 3D printing electrodes, and relates to a novel conductive polymer modified 3D printing electrode, and a preparation method and application thereof.
Background
Chlorogenic acid (CGA) is present in various fruit, vegetable and tea products and ingestion of more than 7mg/kg can lead to serious diseases such as sensitization, oxidative stress, vomiting, inflammatory nausea, dermatitis. Therefore, the most direct, accurate assay is necessary to closely monitor the quantity limitations and quality of CGA. In practical application, the detection of CGA mainly adopts various common methods such as ultra-high performance chromatography, spectrum, liquid chromatography-mass spectrometry, capillary electrophoresis and the like, and the method has high cost, long time consumption and low sensitivity, and often needs a large amount of solvent.
In contrast, the electrochemical method for detecting the CGA has the advantages of being environment-friendly, low in cost, high in sensitivity, quick in response, low in detection limit, good in reproducibility and the like. Although various modified electrodes are used for detecting CGA, the preparation process is complicated, the cost is high, the linear range is narrow, and electrode materials capable of well improving the defects of the electrodes are required to be manufactured.
Therefore, the 3D printing electrode is required to be modified by using PEDOT: PSS, so that chlorogenic acid content can be detected in an actual sample, and the application range of the 3D printing electrode in an electrochemical sensor is effectively widened.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a novel conductive polymer modified 3D printing electrode; the second purpose of the invention is to provide a preparation method of the novel conductive polymer modified 3D printing electrode; the invention further aims to provide an application of the novel conductive polymer modified 3D printing electrode in chlorogenic acid detection.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a preparation method of a novel conductive polymer modified 3D printing electrode, which comprises the following steps:
(1) The activated 3D printing electrode is electrodeposited and modified in hydrochloric acid with the concentration of 0.4-0.6M and tetrachloro-gold acid solution with the concentration of 40-50 mM, and after being cleaned by ultrapure water, the 3D printing electrode (Au@3DE) decorated by gold can be obtained by blowing nitrogen;
(2) Dripping SACP precursor solution on the surface of the gold-modified 3D printing electrode (Au@3DE) by a drop casting method, and air-drying at room temperature to obtain the novel conductive polymer-modified 3D printing electrode (SACP@Au@3DE);
in step (2), the SACP precursor solution is prepared as follows: SMS solution formed by ultrasonic dispersion of beta-cyclodextrin (beta-CD) and citric acid in water and polymer solution formed by mixing glutaraldehyde solution and polyvinyl alcohol (PVA) water solution as cross-linking agent are added into poly 3, 4-dioxyethyl thiophene-poly (p-styrenesulfonic acid) (PEDOT: PSS) water solution, and SACP precursor solution is obtained after stirring at a rotating speed of 1000-1200 rpm.
Preferably, the 3D printing electrode is a graphene/polylactic acid (PLA) 3D printing electrode;
the specific method for activating comprises the following steps: the exposed 3D printing electrode is soaked in NaOH solution with the concentration of 1M for 0.5 to 1 hour, is washed by water to eliminate polylactic acid remained on the surface of the electrode, is dried for 1 to 1.5 hours at the temperature of 50 to 60 ℃, is then activated for 300 to 400 seconds by using 2 to 3V potential in Phosphate Buffer Solution (PBS) with the concentration of 0. M, pH =7.2, and then the activated 3D printing electrode is obtained.
Preferably, the specific method for electrodeposition modification comprises the following steps: the activated 3D printing electrode is deposited for 180-300 s in hydrochloric acid with the concentration of 0.4-0.6M and tetrachloro-gold acid solution with the concentration of 40-50 mM at a constant potential of 0.8-1V.
Preferably, the mass ratio of the beta-cyclodextrin (beta-CD), the citric acid and the ultrapure water in the SMS solution is 0.29-0.3:0.45-0.55:2.47.
Preferably, the mass ratio of the polyvinyl alcohol (PVA) in the polymer solution to glutaraldehyde in the glutaraldehyde solution is 0.06-1:0.54, g;
the mass concentration of glutaraldehyde in the glutaraldehyde solution is 50%.
Preferably, the mass concentration of the polyvinyl alcohol (PVA) in the aqueous solution of the polyvinyl alcohol (PVA) is 8-10%.
Preferably, the mass concentration of the poly 3, 4-dioxyethyl thiophene-poly-p-styrenesulfonic acid (PEDOT: PSS) in the poly 3, 4-dioxyethyl thiophene-poly-p-styrenesulfonic acid (PEDOT: PSS) aqueous solution is 1.0-1.3%.
Preferably, the volume mass ratio of the SMS solution, the polymer solution and the poly (3, 4-dioxyethyl thiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) aqueous solution is 0.16-0.17:0.02-0.04:1.8-1.9, and the ratio is mL: g.
2. A novel conductive polymer modified 3D printing electrode prepared according to the above described method.
3. The application of the novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) in electrochemical detection of chlorogenic acid.
The invention has the beneficial effects that: the invention discloses a preparation method of a novel conductive polymer modified 3D printing electrode, which is mainly characterized in that an SMS solution (beta-cyclodextrin (beta-CD) and citric acid are formed by ultrasonic dispersion in water), a polymer solution (polymer network and glutaraldehyde are formed under the condition that a polyvinyl alcohol (PVA) water solution is used as a cross-linking agent) and a poly (3, 4-dioxyethyl thiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) water solution are stirred to form a SACP precursor solution, and the SACP precursor solution) is dropwise added on the surface of a gold modified 3D printing electrode (Au@3DE) through a drop casting method to form the novel conductive polymer modified 3D printing electrode.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is a scanning electron microscope image of different materials, wherein A is a graphene/PLA 3D printing electrode (Bare-3 DE) which is not subjected to modification treatment, B is an Activated 3D printing electrode (Activated-3 DE), C is a gold modified 3D printing electrode (Au@3DE), and D is a novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) prepared in example 1;
FIG. 2 shows XPS spectra of different materials (A is unmodified graphene/PLA 3D printing electrode (Bare-3 DE), B is Activated 3D printing electrode (Activated-3 DE), C is gold modified 3D printing electrode (Au@3DE), D is novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) prepared in example 1);
FIG. 3 is CV (A) and EIS (B) of the novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) prepared in example 1 were further studied by CV and EIS;
FIG. 4 is a CV curve of redox reaction during electrochemical detection;
fig. 5 is a graph showing the linear relationship between current and chlorogenic acid during electrochemical detection.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
The preparation method of the novel conductive polymer modified 3D printing electrode specifically comprises the following steps:
(1) 2.4g of polyvinyl alcohol (PVA-1799) is weighed and dissolved in 21.6mL of ultrapure water, and is stirred and mixed for 5 hours at 80 ℃ at a rotating speed of 800rpm to obtain a polyvinyl alcohol (PVA) aqueous solution;
(2) Taking 0.295g of beta-cyclodextrin (beta-CD) and 0.5g of citric acid as solvents and taking 2.47g of ultrapure water, and carrying out ultrasonic treatment until the solution is uniformly dispersed to obtain an SMS solution;
(3) Mixing 0.06g of the aqueous solution of polyvinyl alcohol (PVA) obtained in the step (1) with 1. Mu.L of a glutaraldehyde solution having a concentration of 50% to obtain a polymer solution;
(4) 0.165mL of SMS solution and 0.03g of polymer solution were added to 1.875g of an aqueous solution of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) in which the mass concentration of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) was 1.0%, and after stirring vigorously (at 1100 rpm) for 10 minutes, a SACP precursor solution was obtained;
(5) Immersing the bare graphene/PLA 3D printing electrode in 5mL of NaOH solution with the concentration of 1M for 0.5h, washing with water to eliminate polylactic acid remained on the surface, drying the electrode at 50 ℃ for 1h, then placing the electrode in phosphate buffer solution (PBS buffer solution) with the concentration of 0. M, pH =7.2, and activating the electrode for 300s by using 2.5V potential to obtain an activated 3D printing electrode;
(6) Electrodepositing the activated 3D printing electrode in hydrochloric acid with the concentration of 0.5M and tetrachloro-gold acid solution with the concentration of 50mM (constant potential of 0.9V and deposition time of 240 s) for modification, then cleaning the gold-modified electrode (Au@3DE) with ultrapure water, and drying with nitrogen to obtain the gold-modified 3D printing electrode (Au@3DE);
(7) And (3) respectively dripping 5 mu L of SACP precursor solution obtained in the step (4) into the front and back sides of the gold-modified 3D printing electrode (Au@3DE) obtained in the step (6), and drying in air at room temperature to successfully prepare the novel conductive polymer-modified 3D printing electrode (SACP@Au@3DE).
Example 2
The preparation method of the novel conductive polymer modified 3D printing electrode specifically comprises the following steps:
(1) 8.0g of polyvinyl alcohol (PVA-1799) is weighed and dissolved in 92mL of ultrapure water, and is stirred and mixed for 5 hours at 80 ℃ and a rotating speed of 800rpm to obtain a polyvinyl alcohol (PVA) aqueous solution;
(2) Taking 0.29g of beta-cyclodextrin (beta-CD) and 0.55g of citric acid as solvents and taking 2.47g of ultrapure water, and carrying out ultrasonic treatment until the solution is uniformly dispersed to obtain an SMS solution;
(3) Mixing 1.0g of the aqueous solution of polyvinyl alcohol (PVA) obtained in the step (1) with 1.08. Mu.L of a glutaraldehyde solution having a concentration of 50% to obtain a polymer solution;
(4) 0.17mL of SMS solution and 0.02g of polymer solution were added to 1.9g of an aqueous solution of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) in which the mass concentration of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) was 1.2%, and after stirring vigorously (at 1200 rpm) for 10 minutes, a SACP precursor solution was obtained;
(5) Immersing the bare graphene/PLA 3D printing electrode in 5mL of NaOH solution with the concentration of 1M for 1.0h, washing with water to eliminate polylactic acid remained on the surface, drying the electrode at 60 ℃ for 1.5h, then placing the electrode in phosphate buffer solution (PBS buffer solution) with the concentration of 0.1M, pH =7.2, and activating the electrode for 300s by using 2.5V potential to obtain an activated 3D printing electrode;
(6) Electrodepositing the activated 3D printing electrode in hydrochloric acid with the concentration of 0.6M and tetrachloro-gold acid solution with the concentration of 50mM (constant potential of 0.9V and deposition time of 240 s) for modification, then cleaning the gold-modified electrode (Au@3DE) with ultrapure water, and drying with nitrogen to obtain the gold-modified 3D printing electrode (Au@3DE);
(7) And (3) respectively dripping 5 mu L of SACP precursor solution obtained in the step (4) into the front and back sides of the gold-modified 3D printing electrode (Au@3DE) obtained in the step (6), and drying in air at room temperature to successfully prepare the novel conductive polymer-modified 3D printing electrode (SACP@Au@3DE).
Example 3
The preparation method of the novel conductive polymer modified 3D printing electrode specifically comprises the following steps:
(1) 10.0g of polyvinyl alcohol (PVA-1799) is weighed and dissolved in 90mL of ultrapure water, and is stirred and mixed for 5 hours at 80 ℃ and a rotating speed of 800rpm to obtain a polyvinyl alcohol (PVA) aqueous solution;
(2) Taking 2.47g of ultrapure water as a solvent for 0.3g of beta-cyclodextrin (beta-CD) and 0.45g of citric acid, and carrying out ultrasonic treatment until the solution is uniformly dispersed to obtain an SMS solution;
(3) Mixing 0.06g of the aqueous solution of polyvinyl alcohol (PVA) obtained in the step (1) with 1.08. Mu.L of a glutaraldehyde solution having a concentration of 50% to obtain a polymer solution;
(4) 0.16mL of SMS solution and 0.04g of polymer solution were added to 1.8g of an aqueous solution of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) in which the mass concentration of poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) was 1.3%, and after stirring vigorously (at 1000 rpm) for 10 minutes, a SACP precursor solution was obtained;
(5) Immersing the bare graphene/PLA 3D printing electrode in 5mL of NaOH solution with the concentration of 1M for 0.5h, washing with water to eliminate polylactic acid remained on the surface, drying the electrode at 50 ℃ for 1h, then placing the electrode in phosphate buffer solution (PBS buffer solution) with the concentration of 0. M, pH =7.2, and activating the electrode for 300s by using 2.5V potential to obtain an activated 3D printing electrode;
(6) Electrodepositing the activated 3D printing electrode in hydrochloric acid with the concentration of 0.4M and tetrachloro-gold acid solution with the concentration of 40mM (constant potential of 0.9V and deposition time of 240 s) for modification, then cleaning the gold-modified electrode (Au@3DE) with ultrapure water, and drying with nitrogen to obtain the gold-modified 3D printing electrode (Au@3DE);
(7) And (3) respectively dripping 5 mu L of SACP precursor solution obtained in the step (4) into the front and back sides of the gold-modified 3D printing electrode (Au@3DE) obtained in the step (6), and drying in air at room temperature to successfully prepare the novel conductive polymer-modified 3D printing electrode (SACP@Au@3DE).
Performance testing
The surface morphology of different materials is observed by a scanning electron microscope, and the results are shown in fig. 1, wherein A is a graphene/PLA 3D printing electrode (Bare-3 DE) which is not subjected to modification treatment, B is an Activated 3D printing electrode (Activated-3 DE), C is a gold modified 3D printing electrode (Au@3DE), and D is a novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) prepared in the embodiment 1. As can be seen from fig. 1, after the nonconductive PLA is removed under NaOH corrosion, the graphene nanofibers are exposed, a large number of cavities are obviously formed in the activated electrode, the surface area is obviously increased, and the surface of the electrode is completely covered by PEDOT: PSS after modification by a drop casting method. The main elements in the Bare-3DE and the Activated-3DE are C and O respectively, and S2 p is a typical element of PEDOT: PSS, which shows that the preparation method of the embodiment 1 does successfully construct the SACP@Au@3DE modified by the PEDOT: PSS.
FIG. 2 shows XPS spectra of different materials (A is unmodified graphene/PLA 3D printing electrode (Bare-3 DE), B is Activated 3D printing electrode (Activated-3 DE), C is gold modified 3D printing electrode (Au@3DE), D is novel conductive polymer modified 3D printing electrode (SACP@Au@3DE) prepared in example 1). It can be further demonstrated from FIG. 2 that the product prepared in example 1 of the present invention is indeed Au and PEDOT: PSS modified novel conductive polymer modified 3D printed electrode (SACP@Au@3DE).
The electrochemical characteristics of the novel conductive polymer modified 3D printing electrode (sacp@au@3de) prepared in example 1 were further studied by CV and EIS, as shown in fig. 3 a and B, respectively. As can be seen from fig. 3, for Activated 3DE (Activated-3 DE), the redox peak current greatly increased after removal of the non-conductive PLA due to the conductive graphene nanofiber exposure; the electron transfer capability of the Activated-3DE is further enhanced after PEDOT is adsorbed to PSS; the charge transfer resistance of Bare-3DE is relatively large. As expected, activated 3DE (Activated-3 DE) exhibited a lower charge transfer resistance due to the exposure of the conductive graphene nanofibers. After PEDOT: PSS modification of Activated-3DE, the charge transfer resistance was significantly reduced, and these results were consistent with the CV results described above. In summary, the electrochemical performance of the 3D printing electrode is gradually improved by activation and modification of PEDOT: PSS.
Chlorogenic acid with the concentration of 10-400 mu M is placed in an electrochemical detection device (wherein a working electrode in the device is SACP@Au@3DE, a reference electrode is silver chloride, a counter electrode is a platinum wire electrode, and an electrolyte is 0.1M phosphate buffer solution), and the electrocatalytic oxidation reaction of the device is shown in figure 4. Since CGA has a 1, 2-dihydroxybenzene moietyThe oxidation of the compound should therefore form the respective o-quinone and release two electrons and two protons, which can be detected by the electrochemical workstation. In the above detection process, the oxidation peak current increases with the increase of chlorogenic acid (CGA) concentration to form a linear calibration graph of chlorogenic acid (CGA) concentration and oxidation peak current, as shown in FIG. 5 (the linear relationship is y=0.30550x+199.09, R 2 =0.995, where y is current (in μa), x is chlorogenic acid (CGA) concentration (in μm)).
Based on this, actual sample testing was performed on the proposed CGA sensor by using a coffee powder sample. 10mg of coffee powder sample was dispersed in a solution formed by mixing ethanol and deionized water in a volume ratio of 9:1 at a temperature of 90 ℃ for 2 hours, followed by sonication for 2 hours and filtration, and a standard addition amount of 5mg of chlorogenic acid (CGA) was added to the resulting solution. In addition, the prepared real sample was subjected to a reaction at 50mV s -1 To a 0.1M PBS (ph=7.2) buffer solution. The result shows that in the ZnO@PEDOT: PSS-GCE, the reaction is remarkable after the real sample is added, and the recovery rate reaches 95.46-100.3%. Thus, it was demonstrated that the 3D printed electrode (sacp@au@3de) prepared according to the present invention could indeed be used for electrochemically detecting the concentration of chlorogenic acid (CGA).
Similarly, the 3D printing electrodes (sacp@au@3de) prepared in example 2 and example 3 were subjected to corresponding tests, and the results were similar to those of the 3D printing electrode (sacp@au@3de) prepared in example 1.
In summary, the invention discloses a preparation method of a novel conductive polymer modified 3D printing electrode, which is mainly characterized in that an SMS solution (beta-cyclodextrin (beta-CD) and citric acid are formed by ultrasonic dispersion in water), a polymer solution (polymer network and glutaraldehyde (50% GA) are formed by taking a polyvinyl alcohol (PVA) aqueous solution as a cross-linking agent) and a poly (3, 4-dioxyethyl thiophene) -poly (p-styrenesulfonic acid) (PEDOT: PSS) aqueous solution are stirred to form a SACP precursor solution, and the SACP precursor solution) is dropwise added on the surface of a gold modified 3D printing electrode (Au@3DE) through a drop casting method to form the novel conductive polymer modified 3D printing electrode.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the novel conductive polymer modified 3D printing electrode is characterized by comprising the following steps of:
(1) Electrodepositing and modifying the activated 3D printing electrode in hydrochloric acid with the concentration of 0.4-0.6M and tetrachloro-gold acid solution with the concentration of 40-50 mM, cleaning with ultrapure water, and drying with nitrogen to obtain a gold-modified 3D printing electrode;
(2) Dripping SACP precursor solution on the surface of the gold-modified 3D printing electrode by a drop casting method, and air-drying at room temperature to obtain a novel conductive polymer-modified 3D printing electrode;
in step (2), the SACP precursor solution is prepared as follows: and adding an SMS solution formed by ultrasonic dispersion of beta-cyclodextrin and citric acid in water and a polymer solution formed by mixing glutaraldehyde solution and polyvinyl alcohol aqueous solution as a cross-linking agent into the poly (3, 4-dioxyethyl thiophene) -poly (p-styrenesulfonic acid) aqueous solution, and stirring at a rotating speed of 1000-1200 rpm to obtain a SACP precursor solution.
2. The method of claim 1, wherein the 3D printing electrode is a graphene/polylactic acid 3D printing electrode;
the specific method for activating comprises the following steps: the exposed 3D printing electrode is soaked in NaOH solution with the concentration of 1M for 0.5 to 1 hour, is washed by water to eliminate polylactic acid remained on the surface of the electrode, is dried for 1 to 1.5 hours at the temperature of 50 to 60 ℃, is then activated for 300 to 400 seconds by using 2 to 3V potential in phosphate buffer solution with the concentration of 0. M, pH =7.2, and then the activated 3D printing electrode is obtained.
3. The preparation method according to claim 1, wherein the specific method of electrodeposition modification is as follows: the activated 3D printing electrode is deposited for 180-300 s in hydrochloric acid with the concentration of 0.4-0.6M and tetrachloro-gold acid solution with the concentration of 40-50 mM at a constant potential of 0.8-1V.
4. The method according to claim 1, wherein the mass ratio of beta-cyclodextrin, citric acid and ultrapure water in the SMS solution is 0.29-0.3:0.45-0.55:2.47.
5. The preparation method according to claim 1, wherein the mass ratio of polyvinyl alcohol in the polymer solution to glutaraldehyde in the glutaraldehyde solution is 0.06-1:0.54, g:g;
the mass concentration of glutaraldehyde in the glutaraldehyde solution is 50%.
6. The method according to claim 1, wherein the mass concentration of the polyvinyl alcohol in the aqueous solution of the polyvinyl alcohol is 8 to 10%.
7. The preparation method according to claim 1, wherein the mass concentration of the poly 3, 4-dioxyethylthiophene-poly-p-styrenesulfonic acid in the aqueous solution of the poly 3, 4-dioxyethylthiophene-poly-p-styrenesulfonic acid is 1.0-1.3%.
8. The preparation method according to claim 1, wherein the volume mass ratio of the SMS solution, the polymer solution and the poly (3, 4-dioxyethylthiophene) -poly (p-styrenesulfonic acid) aqueous solution is 0.16-0.17:0.02-0.04:1.8-1.9, and the ratio is mL: g.
9. A novel conductive polymer modified 3D printed electrode prepared according to the method of any one of claims 1 to 8.
10. Use of the novel conductive polymer modified 3D printed electrode of claim 9 in electrochemical detection of chlorogenic acid.
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| CN117487298A (en) * | 2023-12-18 | 2024-02-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Electrode material, electrode and flexible sensor |
| CN117487298B (en) * | 2023-12-18 | 2024-04-12 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Electrode material, electrode and flexible sensor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117487298A (en) * | 2023-12-18 | 2024-02-02 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Electrode material, electrode and flexible sensor |
| CN117487298B (en) * | 2023-12-18 | 2024-04-12 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Electrode material, electrode and flexible sensor |
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