CN113588753A - Ion selective electrode current detection method - Google Patents
Ion selective electrode current detection method Download PDFInfo
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- 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
- G01N27/333—Ion-selective electrodes or membranes
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- 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
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- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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Abstract
The invention relates to the field of electrochemical sensors, in particular to a current detection method of an ion selective electrode. And (3) using the redox probe as an indication, and realizing the quantitative detection of the ions to be detected according to the activity (concentration) of the ions to be detected and the current signal change of the redox probe. According to the invention, the redox probe is used for indicating a potential signal of the ion selective electrode, and the relationship between the ion activity and the potential signal in the Nernst equation is converted into the relationship between the ion activity and a current signal, so that the amplification of the signal and the high-sensitivity measurement of the ion are realized.
Description
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a current detection method of an ion selective electrode.
Background
The ion selective electrode is an important branch of the electrochemical sensor, and the detection principle is based on the relationship between the response potential of the sensitive membrane and the ion activity of the analyte, which conforms to Nernst's equation (chem. Rev.108(2008) 329-351). Compared with other detection technologies, the ion selective electrode has the characteristics of good selectivity, high response speed, capability of detecting ion concentration change in situ in real time and the like, and has incomparable advantages in the aspect of ion analysis (Sci. Total environ.537(2015) 453-461). However, the resolution of the measured potential signal is only up to 0.1mV, calculated as Nernst slope (59.1/n mV/dec, n being the number of charges), with a deviation of about 0.4% (monovalent ions), 0.7% (divalent ions) and 1.2% (trivalent ions) in measured ion activity per 0.1mV change in potential. This means that the conventional potential signal measurement of minute ion concentration changes is insufficient, that is, the sensitivity and precision of the potential signal need to be further improved.
Unlike the mV level potential signal, the current signal can be measured to pA level (anal. chem.88(2016) 9850-. Many current-controlled ion-selective electrodes have been reported to achieve the purposes of reversibility (anal. chem.82(2010)1612-1615), low detection limit (anal. chem.acta 707(2011)1-6), simultaneous detection of multiple ions (anal. chem.87(2015)7729-7737), and the like. However, there are few reports of techniques for reading out the ion-selective electrode potential response using current as an output signal, and the coulometric analysis technique proposed by the Bobacka project group obtains the coulometric signal (anal. chem.88(2016)4369-4374) by integrating the instantaneous current to read out the electrode potential response. Although this technique can measure small concentration variations, it is limited by the type of solid-contact conductive layer and the thickness of the ion-selective sensitive film, and if not strictly controlled, the response time of the coulomb signal is long and does not favor rapid measurement. Therefore, there is a need to develop a versatile, simple-to-operate, fast-response ion selective electrode current detection technique.
Disclosure of Invention
The object of the present invention is to develop a method for detecting the current of an ion-selective electrode.
In order to achieve the purpose, the invention adopts the technical scheme that:
a current detection method of an ion selective electrode utilizes an oxidation-reduction probe as an indication to realize the quantitative detection of ions to be detected according to the activity (concentration) of the ions to be detected and the current signal change of the oxidation-reduction probe.
A three-electrode system is adopted, constant voltage is applied between a reference electrode and a working electrode, and the activity (concentration) of ions to be detected causes the potential signal of the reference electrode to change, so that the voltage on the working electrode changes, and the current of the redox probe changes; the quantitative detection of the ions to be detected is realized by detecting the current signal of the redox probe on the working electrode.
The three-electrode system consists of a working electrode, a reference electrode and a counter electrode; wherein the reference electrode is an ion selective electrode.
Further, a three-electrode system is adopted, a working electrode and a redox probe are added into a redox system pool, an ion selective electrode is inserted into a sample pool to be detected, the redox system pool is connected with the sample pool to be detected through a salt bridge, constant voltage is applied between the ion selective electrode and the working electrode, specific identification of ions to be detected and the ion selective electrode in the sample pool causes potential change, the potential change of the ion selective electrode enables the voltage on the working electrode to change, and the current of the redox probe is enabled to change; and further, the quantitative detection of the ions to be detected is realized by detecting the current signal of the redox probe on the working electrode.
The constant voltage applied between the ion selective electrode and the working electrode is: -1.0- + 1.0V.
The redox probe is a potassium ferricyanide/potassium ferrocyanide anion probe, a hexaammonium trichloro ruthenium cation probe or a ferrocene derivative.
The working electrode is a bare gold electrode, a bare glassy carbon electrode, a gold electrode modified by nano materials or a glassy carbon electrode; wherein the nano material is carbon nano tube, graphene or graphite alkyne; the counter potential is a platinum sheet electrode, a platinum wire electrode or a platinum mesh electrode.
The ion selective electrode is composed of a conductive substrate, a solid contact conductive layer and an ion selective sensitive membrane
The conductive substrate is a gold electrode, a glassy carbon electrode or a screen printing electrode; the solid contact conducting layer is a carbon nano tube, graphene, polyaniline, polypyrrole, polythiophene or nano porous gold; the ion selective sensitive membrane consists of an ion carrier, an ion exchanger, a polymer membrane matrix and a plasticizer.
The mass percent concentration of the polymer matrix material in the ion selective sensitive membrane is 10-80%, the mass percent concentration of the plasticizer is 10-80%, the mass percent concentration of the lipophilic ion exchanger is 0.1-10%, and the mass percent of the ion carrier is 0.1-10%; the solvent is tetrahydrofuran.
A current detection system of an ion selective electrode adopts a three-electrode system, an oxidation-reduction system pool and a sample pool to be detected, wherein the three-electrode system consists of a working electrode, a reference electrode and a counter electrode; the reference electrode is an ion selective electrode, the working electrode and the redox probe are added into a redox system pool, the ion selective electrode is inserted into a sample pool to be detected, the redox system pool is connected with the sample pool to be detected through a salt bridge, and constant voltage is applied between the ion selective electrode and the working electrode.
The salt bridge is prepared by mixing gelatinous agar and potassium chloride and then placing the mixture in a U-shaped pipe, wherein the concentration of the potassium chloride is 3-4.2M.
The invention has the following advantages: (1) the invention reads potential signals by using high-sensitivity current signals, thereby realizing signal amplification and high-sensitivity measurement; (2) the current signal of the invention does not follow the limitation of Nernst equation; (3) the sensitivity of the current signal can be further improved by modifying the surface of the electrode, and adjusting the specific surface area and the conductivity of the electrode; (4) the redox probe adopted by the current signal is easy to obtain and configure, and has more universality; (5) compared with coulometry, the response time of the current signal is faster.
Drawings
FIG. 1 is a diagram of an apparatus for an ion selective electrode current detection method according to an embodiment of the present invention (where 1 is a working electrode, 2 is an ion selective electrode, 3 is a counter electrode, 4 is a constant voltage applied between the working electrode 1 and the ion selective electrode 2, 5 is a redox probe generating a current signal by redox reaction at 1, 6 is an ion exchange at 2 generating a potential response, 7 is a current signal at 5 reading a potential signal at 6, 8 is a salt bridge, and 9 is a spacer separating the working electrode 1 and the counter electrode 3 from the ion selective electrode 2.)
Fig. 2 is a graph showing the change of the bare glass carbon electrode potential with the calcium ion concentration when the solid contact type calcium ion selective electrode provided by the embodiment of the invention is used as a reference electrode.
FIG. 3 is a graph showing the current versus voltage variation of a potassium ferricyanide redox probe on a bare glassy carbon electrode according to an embodiment of the present invention.
Fig. 4 is a real-time graph of the current on the bare glassy carbon electrode of the potassium ferricyanide redox probe according to the embodiment of the present invention as the calcium ion concentration changes.
FIG. 5 is a graph of the current on a bare glassy carbon electrode corrected for changes in calcium ion concentration for a potassium ferricyanide redox probe provided in an embodiment of the invention.
FIG. 6 is a graph of the calibration of the current on a bare glassy carbon electrode with a hexaammonium trichloride ruthenium redox probe according to the present invention.
Fig. 7 is a calibration curve diagram of the current of the potassium ferricyanide redox probe on the graphene modified glassy carbon electrode according to the embodiment of the present invention, which is along with the change of the calcium ion concentration.
Detailed Description
The present invention is described in further detail with reference to the following detailed description, but the scope of the present invention is not limited thereto. The materials, reagents and apparatus used in the following examples, which are not specifically illustrated, are conventional in the art and are commercially available to those skilled in the art.
The invention establishes a relation by utilizing the ion activity (concentration) and the current signal of the redox probe, realizes the high-sensitivity measurement of ions, further changes the ion activity (concentration) in the solution to be measured, realizes the potential signal change of the ion selective electrode, further changes the applied voltage on the working electrode, and promotes the current of the redox probe to change; the method specifically comprises the following steps: specifically, a three-electrode system is utilized, an ion selective electrode is connected with a working electrode and a counter electrode, constant voltage is applied between the ion selective electrode and the working electrode, and a current signal of an oxidation-reduction probe on the working electrode is detected;
according to the invention, the redox probe is used for indicating a potential signal of the ion selective electrode, and the relationship between the ion activity and the potential signal in the Nernst equation is converted into the relationship between the ion activity and a current signal, so that the amplification of the signal and the high-sensitivity measurement of the ion are realized.
Example 1
And (3) characterization of the potential of the bare glass carbon electrode along with the change of the calcium ion concentration when the solid contact type calcium ion selective electrode is used as a reference electrode. The method specifically comprises the following steps:
(1) taking two glassy carbon electrodes, respectively adopting 0.05 mu m Al2O3Grinding the powder until the surface of the electrode presents a bright mirror surface, and sequentially ultrasonically cleaning the electrode in ultrapure water, ethanol and ultrapure water to be used as a working electrode or an ion selective electrode substrate for later use;
(2) dripping 60 mu L of ordered mesoporous carbon solution (3mg/mL) on the glassy carbon electrode in the step (1), and drying at room temperature to obtain the ordered mesoporous carbon modified glassy carbon electrode;
(3) weighing 4.14mg of N, N, N ', N' -tetracyclohexyl-3-oxaglutaramide, 4.32mg of sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, 57.24mg of polyvinyl chloride and 110 mu L of 2-nitrophenyloctyl ether, and dissolving the sodium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate, the polyvinyl chloride and the 110 mu L of 2-nitrophenyloctyl ether in 2mL of tetrahydrofuran to prepare a calcium ion selective sensitive membrane solution;
(4) dripping 90 μ L of the solution obtained in the step (3) on the electrode obtained in the step (2), drying at room temperature to volatilize tetrahydrofuran, and preparing the solid contact type calcium ion selective electrode, wherein the electrode is arranged at 1.0 × 10-3M CaCl2Activating in the solution overnight for later use;
(5) placing the glassy carbon working electrode treated in the step (1) as a working electrode, a platinum wire counter electrode and a 5mM potassium ferricyanide/potassium ferrocyanide solution inThe solid contact type calcium ion selective electrode 10 in the step (4) is used as an oxidation-reduction system pool, namely a beaker 1-2The M NaCl solution is placed in a pool to be detected, namely a beaker 2, and the beaker 1 and the beaker 2 are connected by adopting a salt bridge, wherein the salt bridge is prepared by placing a solution prepared from 1g of agar, 10g of potassium chloride and 33ml of deionized water in a 10-centimeter U-shaped tube.
(6) The three electrodes in step (5) were connected to the CHI660C electrochemical workstation, the calcium ion concentration in beaker 2 was gradually increased, and the potential response of the glassy carbon electrode was observed using an open circuit potential technique (see FIG. 2).
As shown in fig. 2, the glassy carbon electrode potential gradually decreased with an increase in the calcium ion concentration. The results show that the potential of the glassy carbon electrode can be changed by adjusting the potential of the solid contact type calcium ion selective electrode.
Example 2
Characterization of the current of the potassium ferricyanide redox probe on the bare glassy carbon electrode as a function of voltage. The method specifically comprises the following steps:
(1) constructed according to the procedure described in example 1, except that in example 1, the apparatus was modified in step (5), and an Ag/AgCl (3M KCl) electrode was placed in a chamber containing 10-2In a beaker 2 of the M NaCl solution, the beaker 1 and the beaker 2 are connected by a salt bridge;
(2) connecting the three electrodes in the step (1) to a CHI660C electrochemical workstation, selecting a multi-potential step technology, and sequentially setting voltage values as follows: 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50V, and the applied time at each voltage was 20s, and the current of the potassium ferricyanide redox probe on the bare glassy carbon electrode was measured as a function of the voltage (see FIG. 3).
As shown in FIG. 3, when an Ag/AgCl (3M KCl) commercial electrode was used as a reference electrode, the current of the potassium ferricyanide redox probe increased with increasing applied voltage and varied linearly in the range of 0.15-0.30V. The result shows that the current change of the potassium ferricyanide redox probe can be realized by adjusting the voltage of the glassy carbon electrode, which lays a foundation for changing the voltage of the glassy carbon electrode by adopting an ion selective electrode subsequently and further realizing the current change of the potassium ferricyanide redox probe.
Example 3
And (3) representing the current change of the potassium ferricyanide redox probe on the bare glass carbon electrode along with the change of the calcium ion concentration. The method specifically comprises the following steps:
(1) the construction was carried out according to the procedure described in example 1 except that the apparatus of step (5) in example 1 was adjusted, a solution of 5mM potassium ferricyanide and potassium ferrocyanide was placed in the beaker 1, the three electrodes were connected to the CHI660C electrochemical workstation, the i-t technique was selected, the voltage between the bare glassy carbon electrode and the calcium ion electrode was set to-0.2V, the calcium ion concentration in the solution was increased stepwise, a real-time response curve of the potassium ferricyanide redox probe current with the change in calcium ion concentration was obtained (FIG. 4), and a corresponding calibration curve was obtained (FIG. 5).
As shown in FIGS. 4 and 5, the current of the potassium ferricyanide redox probe gradually increased with the increase of calcium ion and was at 1.0X 10-5-1.0×10-2The range of the M calcium chloride solution shows a linear response, and the response slope is 24.0 mu A/dec.
Example 4
And (3) representing the current of the hexaammonium trichloride ruthenium redox probe on the bare glass carbon electrode along with the change of the calcium ion concentration. The method specifically comprises the following steps:
(1) the procedure was followed as described in example 1, except that the apparatus in step (5) of example 1 was adjusted, 5mM ruthenium trichlorohexamine solution was placed in beaker 1, the three electrodes were connected to CHI660C electrochemical workstation, i-t technique was selected, the voltage between the bare glassy carbon electrode and the calcium ion electrode was set to-0.5V, the calcium ion concentration in the solution was gradually increased, and a calibration graph of the current of the ruthenium trichlorohexamine redox probe as a function of the calcium ion concentration was obtained (FIG. 6).
As shown in FIG. 6, the current of the ruthenium hexaammonium trichloride redox probe gradually increased with the increase of calcium ion, and was at 1.0X 10-5-1.0×10-2The range of M calcium chloride solution shows linear response, and the response slope is 19.4 mu A/dec. The results show that different types of redox probes can achieve current detection of the ion-selective electrode.
Example 5
And (3) representing the current variation condition of the potassium ferricyanide redox probe on the graphene modified glassy carbon electrode along with the calcium ion concentration. The same as in example 1, except that:
(1) preparing a 1mg/mL graphene oxide solution, dropwise coating 5uL of the graphene oxide solution on a glassy carbon electrode polished in the step (1) in the embodiment 1, drying, taking the graphene oxide modified electrode as a working electrode, Ag/AgCl (3M KCl) as a reference electrode, taking a platinum wire as an auxiliary electrode, connecting the electrode to a three-electrode system of an electrochemical workstation, and scanning a cyclic voltammetry curve in a 10mM disodium hydrogen phosphate and sodium dihydrogen phosphate buffer solution (pH is 5.8) to reduce the graphene oxide, thereby preparing the glassy carbon electrode modified by the reduced graphene oxide, wherein the scanning potential range of the cyclic voltammetry is 0V-1.7V, and the scanning speed is 50 mV/s;
(2) setting up the device in the step (5) in the example 1, placing the glassy carbon working electrode modified by the reduced graphene oxide in the step (1), a platinum wire counter electrode and a 5mM potassium ferricyanide/potassium ferrocyanide solution in a beaker 1, and placing the solid contact type calcium ion selective electrode in the step (4) and the solid contact type calcium ion selective electrode 10-2Placing the M NaCl solution in a beaker 2, and connecting the beaker 1 and the beaker 2 by adopting a salt bridge;
(3) connecting the three electrodes to a CHI660C electrochemical workstation, selecting an i-t technology, setting the voltage between the bare glassy carbon electrode and the calcium ion electrode to be-0.2V, and gradually increasing the concentration of calcium ions in the solution to obtain a correction curve graph (figure 7) of the current of the potassium ferricyanide redox probe on the graphene modified glassy carbon electrode along with the change of the concentration of the calcium ions.
As shown in FIG. 7, the current of the potassium ferricyanide redox probe gradually increased with the increase of calcium ion and was at 1.0X 10-5-1.0×10-2The range of M calcium chloride solution shows linear response, and the response slope is 51.5 mu A/dec. The results indicate that increasing the effective area of the electrode further improves the sensitivity of current detection by the ion-selective electrode.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A current detection method of an ion selective electrode is characterized in that: and (3) using the redox probe as an indication, and realizing the quantitative detection of the ions to be detected according to the activity (concentration) of the ions to be detected and the current signal change of the redox probe.
2. The method for detecting current of an ion selective electrode of claim 1, wherein: a three-electrode system is adopted, constant voltage is applied between a reference electrode and a working electrode, and the activity (concentration) of ions to be detected causes the potential signal of the reference electrode to change, so that the voltage on the working electrode changes, and the current of the redox probe changes; the quantitative detection of the ions to be detected is realized by detecting the current signal of the redox probe on the working electrode.
3. The method for detecting current of an ion selective electrode of claim 2, wherein: the three-electrode system consists of a working electrode, a reference electrode and a counter electrode; wherein the reference electrode is an ion selective electrode.
4. A method of amperometric detection of an ion-selective electrode according to any one of claims 1 to 3, wherein: a three-electrode system is adopted, a working electrode and an oxidation-reduction probe are added into an oxidation-reduction system pool, an ion selective electrode is inserted into a sample pool to be detected, the oxidation-reduction system pool is connected with the sample pool to be detected through a salt bridge, constant voltage is applied between the ion selective electrode and the working electrode, specific identification is carried out on ions to be detected and the ion selective electrode in the sample pool to cause potential change, the potential change of the ion selective electrode enables the voltage on the working electrode to change, and the current of the oxidation-reduction probe is enabled to change; and further, the quantitative detection of the ions to be detected is realized by detecting the current signal of the redox probe on the working electrode.
5. The method for detecting current of an ion selective electrode of claim 4, wherein: the constant voltage applied between the ion selective electrode and the working electrode is: -1.0- + 1.0V.
6. The method for detecting current of an ion selective electrode of claim 4, wherein: the redox probe is a potassium ferricyanide/potassium ferrocyanide anion probe, a hexaammonium trichloro ruthenium cation probe or a ferrocene derivative.
7. The method for detecting current of an ion selective electrode of claim 4, wherein: the working electrode is a bare gold electrode, a bare glassy carbon electrode, a gold electrode modified by nano materials or a glassy carbon electrode; wherein the nano material is carbon nano tube, graphene or graphite alkyne; the counter potential is a platinum sheet electrode, a platinum wire electrode or a platinum mesh electrode.
8. The method for detecting current of an ion selective electrode of claim 4, wherein: the ion selective electrode is composed of a conductive substrate, a solid contact conductive layer and an ion selective sensitive membrane.
9. The method for detecting current of an ion selective electrode of claim 4, wherein: the conductive substrate is a gold electrode, a glassy carbon electrode or a screen printing electrode; the solid contact conducting layer is a carbon nano tube, graphene, polyaniline, polypyrrole, polythiophene or nano porous gold; the ion selective sensitive membrane consists of an ion carrier, an ion exchanger, a polymer membrane matrix and a plasticizer.
10. A current sensing system for an ion selective electrode according to claim 1, wherein: the system adopts a three-electrode system, an oxidation-reduction system pool and a sample pool to be detected, wherein the three-electrode system consists of a working electrode, a reference electrode and a counter electrode; the reference electrode is an ion selective electrode, the working electrode and the redox probe are added into a redox system pool, the ion selective electrode is inserted into a sample pool to be detected, the redox system pool is connected with the sample pool to be detected through a salt bridge, and constant voltage is applied between the ion selective electrode and the working electrode.
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