CN108195909B - Preparation method of planar solid reference electrode - Google Patents
Preparation method of planar solid reference electrode Download PDFInfo
- Publication number
- CN108195909B CN108195909B CN201711326344.1A CN201711326344A CN108195909B CN 108195909 B CN108195909 B CN 108195909B CN 201711326344 A CN201711326344 A CN 201711326344A CN 108195909 B CN108195909 B CN 108195909B
- Authority
- CN
- China
- Prior art keywords
- reference electrode
- planar solid
- solid reference
- kcl
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/301—Reference electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inert Electrodes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparation method of a planar solid reference electrode, which comprises the following steps of (1) printing Ag paste-KCl agar conductive adhesive on a polyester sheet by a screen printing technology, and drying in a dark place; (2) dripping a gold-containing nano graphene suspension (AuNPs/GO) on the surface of the Ag-KCl conducting layer, and airing in a dark place; (3) finally, dripping a PVC solution; (4) drying in the dark at room temperature. The preparation method of the planar solid reference electrode provided by the method is rapid and low in cost, the prepared planar solid reference electrode has long-term stability, and environmental factors (such as inorganic salt, acidity and the like) have small influence on the potential of the planar solid reference electrode, so that the planar solid reference electrode has practical application value.
Description
Technical Field
The invention relates to a preparation method of a planar solid reference electrode, belonging to the technical field of electrochemical analysis in the field of analytical chemistry.
Background
In recent years, electrochemical sensors have been greatly developed in terms of miniaturization, disposability, solidification, and the like. Although Ag/AgCl and Hg/Hg2Cl2Reference electrodes are still widely used, but they have the following disadvantages: the volume is too large; the electrode containing the internal reference solution is not conducive to long-term use, long-distance carrying, use under extreme environmental conditions, and the like. Thus, Ag/AgCl and Hg/Hg2Cl2 reference electrodes are difficult to use with miniaturized equipment and certain specialized methods. This makes the development of miniaturized solid reference electrodes very important.
In general, the solid reference electrode should be provided with a conductive material, a reversible redox buffer system (internal reference solution), a non-ionic selective membrane, etc. to ensure that the electrode potential does not change with changes in the measurement system. The conductive material can reduce the resistance of the electrode and effectively prevent the polarization of the electrode; non-ion selective membranes (e.g., cation-sensitive membranes, polyion-sensitive membranes, silicone rubber membranes, polyurethane membranes, etc.) stabilize the electrode potential of the reference electrode. Rius-Ruiz et al (Rius-Ruiz F X, et al, Analytical and Bioanalytical Chemistry,2011,399 (10): 3613) constructed a carbon nanotube-based polyacrylate membrane solid state reference electrode, but did not detect electrode potential stability. Desmond et al (Desmond D, et al.. Sensors & actors B Chemical,1997,44 (1-3): 389) modified the Ag/AgCl layer or Ag/AgCl + KCl resin film directly on the solid electrode surface to improve the stability of the electrode. Idegami K et al (Idegami K, et al, japan Journal of Applied Physics, 2010, 49(9): 97003) modify a solution containing agar KCl electrolyte on the Ag/AgCl layer, and finally modify a chloroprene protective layer, and were used for pH detection of blood, coca-cola, skim milk, etc. Although each of these solid reference electrodes has its characteristics and applications, it has disadvantages of complicated preparation process, unsatisfactory potential stability, and sensitivity to environmental factors (such as inorganic salts, acidity, etc.), so that the accuracy, reproducibility, and service life of the measurement result of the electrochemical sensor formed by the surface of such solid reference electrode are affected.
Disclosure of Invention
The invention aims to provide a preparation method of a planar solid reference electrode aiming at the defects of the existing preparation method and performance of the solid reference electrode, such as complex preparation process, unsatisfactory potential stability, sensitivity to environmental factors (such as inorganic salt, acidity and the like) and the like, so as to obtain the planar solid reference electrode with less influence of the more ideal potential stability and the environmental factors, and enable the measurement result of an electrochemical sensor formed by the planar solid reference electrode to be more accurate and reliable.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a planar solid reference electrode comprises the following steps: (1) printing Ag paste-KCl agar conductive adhesive on a polyester sheet by a screen printing technology, and drying in the dark; (2) dripping a gold-containing nano graphene suspension (AuNPs/GO) on the surface of the Ag-KCl conducting layer, and airing in a dark place; (3) finally, dripping a PVC solution; (4) drying in the dark at room temperature.
Study of Ag paste-KCl agar conductive adhesive: adding agar into a KCl solution with a certain concentration, heating in an oil bath at 100 ℃ until the agar is completely dissolved to obtain KCl agar sol; and (3) uniformly stirring the KCl agar sol and the silver paste, and performing ultrasonic treatment for 1 hour to obtain the Ag paste-KCl agar conductive adhesive.
The mass ratio of Ag to KCl in the Ag paste-KCl agar conductive adhesive is 1: 0.08.
Research on graphene suspension containing gold nanoparticles: HAuCl4Boiling with trisodium citrate at 105 ℃, and refluxing for 1 h to obtain wine red gold nano sol. And immersing graphene into the prepared gold nano sol, slowly stirring overnight, and freeze-drying to obtain the gold-containing nano graphene composite material. And dispersing the gold-containing nano graphene in a conductive paste diluent, and performing ultrasonic treatment for 30 min to obtain a gold-containing nano graphene suspension.
Further, the solid content of the gold-containing nano graphene suspension is 0.1% -1.0%. Preferably, the solid content in the gold-containing nano-graphene suspension is 0.5%.
Adding a proper amount of PVC and a plasticizer into the tetrahydrofuran solution, and dissolving the mixture by ultrasonic to obtain a PVC film solution.
Further, the concentration of the PVC solution is 1% -5%. Preferably, the concentration of the PVC solution is 3%.
Performance study of planar solid reference electrode: respectively adding 10 into an electrolytic cell-7Inorganic salt solution (KCl, NaCl, CaCl) of mol/L2NH4Cl, PBS buffer, NaNO3，Na2SO4) And slowly stirring, and detecting the potential change of the prepared planar solid reference electrode. Further, the concentration of each inorganic salt was increased to 10 every 600 seconds, respectively-6mol/L、10-5mol/L、10-4mol/L、10-3mol/L、10-2mol/L、10-1And (3) detecting the potential change of the prepared planar solid reference electrode according to the mol/L, wherein the potential of the prepared planar solid reference electrode changes only slightly (1.5-1.8 mV/dec) when the concentration of each substance is changed, and the planar solid reference electrode is recovered to be stable in a short time.
Further, the influence of the acidity of the solution on the potential of the prepared planar solid reference electrode was examined, the pH of a KCl solution adjusted to 0.01 mol/L =3.0, the pH thereof was adjusted to pH =4.0, pH =5.0, pH =6.0, pH =7.0, pH =8.0, pH =9.0, respectively, every 600 s, and the potential change of the prepared planar solid reference electrode at different acidity was examined, it was revealed that the prepared planar solid reference electrode was slightly changed in potential (0.08-0.10 mV/pH) within the above range of acidity and was stabilized in a short time.
Further, the prepared planar solid reference electrode has a potential change value of less than 1.5 mV after being placed for 3 months.
The reagents used in the invention are all analytically pure.
The invention has the following beneficial effects:
the method overcomes the defects of the existing solid reference electrode in the aspects of preparation method and performance, such as complex preparation process, non-ideal potential stability, sensitivity to environmental factors (such as inorganic salt, acidity and the like), and the like, and provides the preparation method of the planar solid reference electrode, which is particularly characterized in that the ① planar solid reference electrode is convenient and quick to prepare and has low cost, the ② prepared planar solid reference electrode is stable in potential, the environmental factors (such as inorganic salt, acidity and the like) have small influence on the potential of the prepared planar solid reference electrode, and the ③ prepared planar solid reference electrode has long-term stability and practical application value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 shows a three-electrode system with a bare glassy carbon electrode as a working electrode, a platinum sheet electrode as a counter electrode, and a prepared planar solid electrode as a reference electrode, at a concentration of 5 × 10-3mol/L [Fe(CN)6]4-Cyclic voltammograms in solution. The scanning potential range is-0.4V-0.8V, the scanning speed is 100 mV/s, and the scanning is carried out for 40 circles.
FIG. 2 shows a three-electrode system consisting of a commercial Ag/AgCl planar solid electrode as a reference electrode and a bare glassy carbon electrode as a working electrode and a platinum sheet electrode as a counter electrode, at a concentration of 5 × 10-3mol/L [Fe(CN)6]4-Cyclic voltammograms in solution. Scanning the potential range-0.4V-0.8V, scanning speed of 100 mV/s, and scanning for 40 circles.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Printing Ag paste-KCl agar conductive adhesive (the mass ratio of Ag to KCl in the Ag paste-KCl agar conductive adhesive is 1: 0.08) on a polyester chip by a screen printing technology, and drying in a dark place; dripping a gold-containing nano graphene suspension with the solid content of 0.5% on the surface of the Ag-KCl conductive layer, and drying in the dark; dripping 3% PVC solution; drying in the dark at room temperature.
10-7mol/L-10-1KCl, NaCl, CaCl in mol/L2，NH4Cl, PBS buffer, NaNO3，Na2SO4The solution had a small effect (1.5-1.8 mV/dec) on the potential stability of the prepared planar solid reference electrode and was stable again in a short time.
When the acidity of the solution was changed in the range of pH =3.0 to pH =9.0, the potential of the prepared planar solid reference electrode was slightly changed (0.08 to 0.10 mV/pH), and was stabilized in a short time.
After the prepared planar solid reference electrode is placed for 3 months, the potential change value is less than 1.5 mV.
The prepared planar solid reference electrode, the bare glassy carbon electrode and the platinum sheet electrode form a three-electrode system with the concentration of 5 × 10-3mol/L [Fe(CN)6]4-In the solution, cyclic voltammetry scanning is carried out at 100 mV/s, the scanning potential range is minus 0.4V to 0.8V, scanning is carried out for 40 circles, as shown in figure 1, meanwhile, a commercial Ag/AgCl electrode is used as a reference electrode, a bare glassy carbon electrode and a platinum sheet electrode form a three-electrode system, and the concentration is 5 × 10-3mol/L [Fe(CN)6]4-The cyclic voltammetry scanning is carried out in the solution at 100 mV/s, the scanning potential range is minus 0.4V to 0.8V, and the scanning is carried out for 40 circles. See fig. 2.
As can be seen from FIGS. 1 and 2, the planar solid reference electrode prepared by the method of the present invention has electrochemical properties similar to those of the commercial Ag/AgCl electrode.
The results show that the method for preparing the planar solid reference electrode has practical application value.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A preparation method of a planar solid reference electrode is characterized by comprising the following steps: the method comprises the following steps: (1) printing Ag paste-KCl agar conductive adhesive on a polyester sheet by a screen printing technology, and drying in the dark; (2) dripping a gold-containing nano graphene suspension (AuNPs/GO) on the surface of the Ag-KCl conducting layer, and airing in a dark place; (3) finally, dripping a PVC solution; (4) drying in the dark at room temperature;
the solid content of the gold-containing nano graphene suspension (AuNPs/GO) is 0.1% -1.0%;
the concentration of the PVC solution is 1% -5%;
the mass ratio of Ag to KCl in the Ag paste-KCl agar conductive adhesive is 1: 0.08.
2. The method for preparing a planar solid reference electrode according to claim 1, wherein: the concentration of the PVC solution is 3%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711326344.1A CN108195909B (en) | 2017-12-13 | 2017-12-13 | Preparation method of planar solid reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711326344.1A CN108195909B (en) | 2017-12-13 | 2017-12-13 | Preparation method of planar solid reference electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108195909A CN108195909A (en) | 2018-06-22 |
| CN108195909B true CN108195909B (en) | 2020-08-04 |
Family
ID=62574401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711326344.1A Active CN108195909B (en) | 2017-12-13 | 2017-12-13 | Preparation method of planar solid reference electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108195909B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915794A (en) * | 2010-07-23 | 2010-12-15 | 浙江大学 | All-solid-state reference electrode and preparation method thereof |
| CN105842313A (en) * | 2016-05-09 | 2016-08-10 | 江苏大学 | Micro-nano textured graphene-based bionic pH sensor and manufacturing method thereof |
| CN106018516A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | Method for preparing graphene modified composite slab pH sensor |
-
2017
- 2017-12-13 CN CN201711326344.1A patent/CN108195909B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101915794A (en) * | 2010-07-23 | 2010-12-15 | 浙江大学 | All-solid-state reference electrode and preparation method thereof |
| CN105842313A (en) * | 2016-05-09 | 2016-08-10 | 江苏大学 | Micro-nano textured graphene-based bionic pH sensor and manufacturing method thereof |
| CN106018516A (en) * | 2016-05-09 | 2016-10-12 | 江苏大学 | Method for preparing graphene modified composite slab pH sensor |
Non-Patent Citations (2)
| Title |
|---|
| All-Solid-State Reference Electrodes Based on Colloid-Imprinted Mesoporous Carbon and Their Application in Disposable Paper-based Potentiometric Sensing Devices;Jinbo Hu 等;《ANALYTICAL CHEMISTRY 》;20150129;第87卷;第2981-2987页 * |
| Disposable Planar Reference Electrode Based on Carbon Nanotubes and Polyacrylate Membrane;F. Xavier Rius-Ruiz 等;《ANALYTICAL CHEMISTRY》;20110531;第83卷;第5783-5788页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108195909A (en) | 2018-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wardak | Solid contact cadmium ion-selective electrode based on ionic liquid and carbon nanotubes | |
| Gyurcsányi et al. | Novel polypyrrole based all-solid-state potassium-selective microelectrodes | |
| CN108318568A (en) | A kind of electrochemical sensor and preparation method for Sensitive Detection heavy metal cadmium ion | |
| O’Hare et al. | Metal–metal oxide pH sensors for physiological application | |
| Zhang et al. | High sensitive on-site cadmium sensor based on AuNPs amalgam modified screen-printed carbon electrodes | |
| Yu et al. | An all-solid-state Cd2+-selective electrode with a low detection limit | |
| Liu et al. | A solid-contact Pb2+-selective electrode based on electrospun polyaniline microfibers film as ion-to-electron transducer | |
| JPH0633063U (en) | Graphite-based solid polymer membrane ion-selective electrode | |
| Kianipour et al. | Room temperature ionic liquid/multiwalled carbon nanotube/chitosan-modified glassy carbon electrode as a sensor for simultaneous determination of ascorbic acid, uric acid, acetaminophen, and mefenamic acid | |
| Yu et al. | A solid-contact Pb2+-selective electrode using poly (2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene vinylene) as ion-to-electron transducer | |
| CN108982641B (en) | Preparation method of electrochemical sensor for trace lead ion detection | |
| CN109001276A (en) | The building and application of electrochemical sensor based on COFs material | |
| Lu et al. | A new solid-state silver ion-selective electrode based on a novel tweezer-type calixarene derivative | |
| Koryta | Ion-selective electrodes | |
| An et al. | Robust single-piece all-solid-state potassium-selective electrode with monolayer-protected Au clusters | |
| Han et al. | Amperometric response of solid-contact ion-selective electrodes utilizing a two-compartment cell and a redox couple in solution | |
| Wang et al. | Thin polymeric membrane ion-selective electrodes for trace-level potentiometric detection | |
| Alva et al. | Ag/AgCl reference electrode based on thin film of arabic gum membrane | |
| Yin et al. | A magnetic field-directed self-assembly solid contact for construction of an all-solid-state polymeric membrane Ca2+-selective electrode | |
| CN111366627B (en) | Covalent organic framework porous structure of capillary tip and preparation method and application thereof | |
| Ma et al. | High-sensitive and selective Eu3+ electrochemical sensor based on LaB6 electrode and sodium dodecylbenzene sulfonate | |
| Hassan et al. | Flow injection analysis of sulfite ion with a potentiometric titanium phosphate–epoxy based membrane sensor | |
| CN108195909B (en) | Preparation method of planar solid reference electrode | |
| Liu et al. | Simple sensor for simultaneous determination of dihydroxybenzene isomers | |
| CN104007154A (en) | Redox hydrosol, and making method and application of integrated microbial electrode used for rapid detection of biotoxicity of water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |