CN112162021A - Modified electrode material, preparation method, modified electrode and application - Google Patents
Modified electrode material, preparation method, modified electrode and application Download PDFInfo
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Images
Classifications
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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
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
-
- 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
- G01N27/36—Glass electrodes
-
- 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
Abstract
The invention relates to a modified electrode material, a preparation method, a modified electrode and application, and belongs to the technical field of electrode material preparation. Graphite powder is used as a raw material and is oxidized, ionic liquid is used as a binder, the composite material of the graphite powder and the ionic liquid is used for preparing a modified carbon paste electrode, the high electrocatalysis of the composite material and the good conductivity, high chemical and thermal stability of the ionic liquid are comprehensively utilized, the composite material and the ionic liquid have high cooperative sensitivity, good stability and certain selectivity, and therefore a novel vitamin detection method and a novel vitamin detection technology are provided, and the method has important significance for detecting vitamins in real samples.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a modified electrode material, a preparation method, a modified electrode and application.
Background
With the improvement of living standard, people pay more and more attention to their health and nutritional needs, and vitamins are a kind of organic compounds necessary for maintaining health. Vitamins are trace organic substances essential for the growth and metabolism of organisms. It is divided into fat-soluble vitamins and water-soluble vitamins. The former includes vitamin A, vitamin D, vitamin E, vitamin K, etc., and the latter includes vitamin B and vitamin C.
The method for quickly and conveniently determining the vitamins in the sample is established, has good application value, and the main methods for determining the vitamins at present comprise a chromatographic method, a photometric method, a fluorescence method and an electrochemical method, wherein the electrochemical method is quicker, simpler and more convenient to determine and has higher sensitivity, so that the electrochemical method is valued for determining the relevant vitamins.
In the preparation of electrochemical biosensors, the selection of the support material is very important, the support material affects the performance of the analyte due to its interaction with the analyte and surface reactions, and the detection requirements are difficult to achieve with a single material due to its own structural or performance limitations.
If two or more than two materials are compounded, the composite material has better comprehensive performance, in the research, the room-temperature ionic liquid consisting of organic cations and anions is a novel non-aqueous polar solvent, and has a plurality of good characteristics, such as negligible vapor pressure, non-inflammability, high ion conductivity, high thermal stability, wide electrochemical window and the like. Therefore, the invention oxidizes graphite powder, takes ionic liquid as a binder to prepare a modified carbon paste electrode, and detects vitamins by an electrochemical method. The method has the advantages of low cost, improved sensitivity, reduced measurement error, and good detection effect on vitamins in blood.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a modified electrode material, a preparation method, a modified electrode and application.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a modified electrode material, the method comprising the steps of:
(1) preparing graphite oxide powder: mixing graphite powder with mixed acid, performing ultrasonic treatment, washing the graphite powder subjected to ultrasonic treatment to weak acidity, and drying for later use;
(2) preparing an ionic liquid composite material: adding ionic liquid into an organic solvent, and ultrasonically mixing uniformly for later use;
(3) preparing a graphite oxide powder/ionic liquid composite material modified electrode material: and ultrasonically and uniformly mixing the graphite oxide powder and the ionic liquid composite material according to the proportion of 0.2-0.6 g to 0.2-1 ml to prepare the modified electrode material.
As a preferred technical scheme, the ratio of the graphite powder to the mixed acid is as follows: 0.2-1 g: 1-3 ml; the ratio of the organic solvent to the ionic liquid is as follows: 0.2-4 g for 1-3 ml.
According to a preferable technical scheme, the mixed acid is a mixed acid of nitric acid and sulfuric acid or a mixed acid of nitric acid and hydrochloric acid, wherein the concentration of hydrochloric acid is 36-38%, the concentration of sulfuric acid is 95-98%, the concentration of nitric acid is 65-68%, and the ratio of nitric acid to hydrochloric acid/sulfuric acid is 2-6: 1-3.
As a preferred technical scheme, when the graphite oxide powder and the ionic liquid composite material are ultrasonically and uniformly mixed according to the proportion of 0.2-0.6 g: 0.2-1 ml, the method specifically comprises the steps of fully and uniformly mixing the graphite powder and mixed acid according to the proportion of 0.2-0.6 g: 0.2-1 ml, and then carrying out ultrasonic treatment to uniformly disperse the graphite powder and the mixed acid.
As a preferred technical scheme, the ionic liquid is a hexafluorophosphate ionic liquid.
Preferably, the organic solvent is any one of DMSO (dimethyl sulfoxide), methanol, acetonitrile, DMF (N, N-dimethylformamide).
The invention also provides the graphite oxide powder/ionic liquid modified electrode material prepared by the preparation method of the modified electrode material.
The invention also provides application of the graphite oxide powder/ionic liquid modified electrode material in a modified electrode.
The invention also provides a preparation method of the modified electrode, wherein the graphite oxide powder/ionic liquid modified electrode material is coated on the electrode and dried to prepare the graphite oxide powder/ionic liquid modified electrode.
The graphite oxide powder/ionic liquid modified electrode is prepared according to the preparation method of the graphite oxide powder/ionic liquid modified electrode.
The invention also provides the application of the graphite oxide powder/ionic liquid modified electrode as a vitamin detection electrode.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares a modified electrode material by oxidizing graphite powder and taking ionic liquid as a binder through the method, and then applies the material on an electrode to prepare a biological electrode sensor for detecting vitamins. The electrode plate sensor manufactured by the method can be used as a disposable consumable for vitamin detection, the cost is low, the electrode plate sensor manufactured by the method has high sensitivity, the measurement error is reduced, and the electrode plate sensor has important significance for directly detecting vitamins in blood.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below. Throughout the drawings, like elements or portions are generally identified by like reference numerals. In the drawings, elements or portions are not necessarily drawn to scale.
FIG. 1 is a regression graph of VB2 sample in example 1 of the present invention;
FIG. 2 is a graph showing the serum test in example 1 of the present invention;
FIG. 3 is a regression graph of VB2 sample in example 2 of the present invention;
FIG. 4 is a graph showing the serum test in example 2 of the present invention;
FIG. 5 is a regression graph of VB2 samples in example 3 of the present invention;
FIG. 6 is a graph showing the serum test in example 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all the directional indicators (such as upper, lower, left, right, front and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
The invention will now be further described with reference to the accompanying drawings.
Example 1:
the preparation method of the graphite oxide powder/ionic liquid modified electrode comprises the following steps:
(1) preparing graphite oxide powder: carrying out ultrasonic treatment on 1g of graphite powder by using 3ml of mixed acid, washing the graphite powder subjected to ultrasonic treatment to weak acidity, and drying for later use;
(2) preparing an ionic liquid composite material: adding 0.2g of hexafluorophosphate ionic liquid into 1ml of DMF (N, N-dimethylformamide), and ultrasonically mixing uniformly for later use;
(3) preparing a graphite oxide powder/ionic liquid modified electrode: 0.2g of graphite oxide powder and 0.4ml of ionic liquid composite material are taken to be mixed evenly by ultrasound, coated on an electrode and dried for standby.
The mixed acid in the step (1) is nitric acid: sulfuric acid (v/v: 4:2), and fully and uniformly mixing graphite powder and mixed acid, and then carrying out ultrasonic treatment to uniformly disperse the graphite powder.
The organic solvent in the step (2) can also be other organic solvents with certain adhesiveness, and the ionic liquid can also be other common ionic liquids.
The test method in the embodiment of the invention takes a three-electrode system as an example, the graphite oxide powder/ionic liquid modified electrode material prepared in the above way is filled into a clean glass tube, a copper wire is inserted as a lead, the modified electrode is prepared by pressing and cooling under balanced pressure, the prepared modified electrode is a working electrode, the reference electrode and the counter electrode are silver wire electrodes, the electrodes are properly heated before use, and the electrodes are pressed and polished for standby.
Measurement of pure product
When the vitamin is measured, a differential pulse method (DPV) is adopted to detect the vitamin, the electrode needs to be pressed and polished before each detection, and a standard curve of samples with different concentrations is shown in figure 1.
Preparing pure products with different concentrations, adding vitamin B2 samples with the volumes of 120 mu L and the concentrations of 1 mu mol/L, 5 mu mol/L, 10 mu mol/L, 20 mu mol/L and 40 mu mol/L into the vitamin B2 diluent, inserting the prepared electrodes into samples to be detected, detecting the vitamin B2 with each concentration by using a differential pulse method (DPV), testing the concentration of the same point in parallel for 5 times according to a corresponding detection program, recording the current value (IP) of each test result of each vitamin, performing linear regression by taking the mean value of the IP value as a horizontal coordinate (x) and the theoretical concentration (y) as a vertical coordinate, and calculating a linear correlation coefficient R2.
As shown in fig. 1, as can be seen from fig. 1, the linear regression equation is y (0.8647 x-0.00261), R2 (0.9979), and the minimum detection concentration (final concentration) of the method is 10nmol/L (modified according to actual results).
Detection of serum
In the measurement of vitamin B2 in serum, the prepared electrode was inserted into the treated serum sample and tested by differential pulse method (DPV), the electrode was pressed and polished before each test, and the test serum pattern is shown in fig. 2, where fig. 2 shows the corresponding current value (ip ═ 0.52) for vitamin B2 in the serum sample. The method is simple to prepare and low in detection limit, and provides a new method for detecting the vitamins in the related samples.
Example 2
The preparation method of the graphite oxide powder/ionic liquid modified electrode comprises the following steps:
(1) preparing graphite oxide powder: carrying out ultrasonic treatment on 1g of graphite powder by using 1ml of mixed acid, washing the graphite powder subjected to ultrasonic treatment to weak acidity, and drying for later use;
(2) preparing an ionic liquid composite material: adding 0.5g of hexafluorophosphate ionic liquid into 0.5ml of DMF, and ultrasonically mixing uniformly for later use;
(3) preparing a graphite oxide powder/ionic liquid modified electrode: 0.3g of graphite oxide powder and 0.8ml of ionic liquid composite material are taken to be mixed evenly by ultrasound, coated on an electrode and dried for standby.
The mixed acid in the step (1) is nitric acid: acid (v/v: 2:3), and fully and uniformly mixing the graphite powder and the mixed acid, and then performing ultrasonic treatment to uniformly disperse the graphite powder.
The organic solvent in the step (2) can also be other organic solvents with certain adhesiveness, and the ionic liquid can also be other common ionic liquids.
The test method in the embodiment of the invention takes a three-electrode system as an example, the graphite oxide powder/ionic liquid modified electrode material prepared in the above way is filled into a clean glass tube, a copper wire is inserted as a lead, the modified electrode is prepared by pressing and cooling under balanced pressure, the prepared modified electrode is a working electrode, the reference electrode and the counter electrode are silver wire electrodes, the electrodes are properly heated before use, and the electrodes are pressed and polished for standby.
Measurement of pure product
When the vitamin is measured, a differential pulse method (DPV) is adopted to detect the vitamin, the electrode needs to be pressed and polished before each detection, and a standard curve of samples with different concentrations is shown in figure 3.
Preparing pure products with different concentrations, wherein the volumes are 120 mu L, and the concentrations areAdding vitamin B2 samples of 1 mu mol/L, 5 mu mol/L, 10 mu mol/L, 20 mu mol/L and 40 mu mol/L into a vitamin B2 diluent, inserting prepared electrodes into a sample to be detected, detecting each concentration of vitamin B2 by using a differential pulse method (DPV), testing the concentration of the same point in parallel for 5 times according to a corresponding detection program, recording the current value (IP) of each vitamin test result, performing linear regression by taking the average value of the IP values as the abscissa (x) and the theoretical concentration (y) as the ordinate, and calculating the linear correlation coefficient R2. The detection data is shown in FIG. 3, wherein Y is 0.8647x-0.0026, R2＝0.9979。
Detection of serum
When measuring vitamin B2 in serum, the prepared electrode is inserted into the treated serum sample, and the difference pulse method (DPV) is used to detect the electrode, the electrode needs to be pressed and polished before each detection, the serum detection graph is shown in figure 4, and the corresponding current value of vitamin B2 detected in the serum sample is reflected in figure 4. The method is simple to prepare, has low detection limit, and provides a new method for detecting vitamins in related samples, wherein Ep is-0.45V, and ip is 0.523039uA in figure 4.
Example 3
The preparation method of the graphite oxide powder/ionic liquid modified electrode comprises the following steps:
(1) preparing graphite oxide powder: carrying out ultrasonic treatment on 1g of graphite powder by using 1ml of mixed acid, washing the graphite powder subjected to ultrasonic treatment to weak acidity, and drying for later use;
(2) preparing an ionic liquid composite material: adding 1.2g of hexafluorophosphate ionic liquid into 0.6ml of DMF, and ultrasonically mixing uniformly for later use;
(3) preparing a graphite oxide powder/ionic liquid modified electrode: 0.2g of graphite oxide powder and 0.8ml of ionic liquid composite material are taken to be mixed evenly by ultrasound, coated on an electrode and dried for standby.
The mixed acid in the step (1) is nitric acid: and (2) acid (v/v: 2-6: 1-3), fully and uniformly mixing the graphite powder and the mixed acid, and then performing ultrasonic treatment to uniformly disperse the graphite powder.
The organic solvent in the step (2) can also be other organic solvents with certain adhesiveness, and the ionic liquid can also be other common ionic liquids.
The test method in the embodiment of the invention takes a three-electrode system as an example, the graphite oxide powder/ionic liquid modified electrode material prepared in the above way is filled into a clean glass tube, a copper wire is inserted as a lead, the modified electrode is prepared by pressing and cooling under balanced pressure, the prepared modified electrode is a working electrode, the reference electrode and the counter electrode are silver wire electrodes, the electrodes are properly heated before use, and the electrodes are pressed and polished for standby.
Measurement of pure product
When the vitamin is measured, a differential pulse method (DPV) is adopted to detect the vitamin, the electrode needs to be pressed and polished before each detection, and a standard curve of samples with different concentrations is shown in figure 5.
Preparing pure products with different concentrations, adding vitamin B2 samples with the volumes of 120 mu L and the concentrations of 1 mu mol/L, 5 mu mol/L, 10 mu mol/L, 20 mu mol/L and 40 mu mol/L into the vitamin B2 diluent, inserting the prepared electrodes into samples to be detected, detecting the vitamin B2 with each concentration by using a differential pulse method (DPV), testing the concentration of the same point in parallel for 5 times according to a corresponding detection program, recording the current value (IP) of each test result of each vitamin, performing linear regression by taking the mean value of the IP value as a horizontal coordinate (x) and the theoretical concentration (y) as a vertical coordinate, and calculating a linear correlation coefficient R2. The detection data is shown in fig. 5, wherein Y is 5.553x +1.145, and R is2＝0.9986。
Detection of serum
When measuring vitamin B2 in serum, the prepared electrode was inserted into the treated serum sample and tested by differential pulse method (DPV), the electrode was pressed and polished before each test, and the test serum pattern is shown in FIG. 6, in which the corresponding current value of vitamin B2 in the serum sample is reflected in FIG. 6. The method is simple to prepare, has low detection limit, and provides a new method for detecting vitamins in related samples, wherein in figure 6, Ep is-0.42V, and ip is 0.392157 uA.
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (10)
1. A preparation method of a modified electrode material is characterized by comprising the following steps:
(1) preparing graphite oxide powder: mixing graphite powder with mixed acid, performing ultrasonic treatment, washing the graphite powder subjected to ultrasonic treatment to weak acidity, and drying for later use;
(2) preparing an ionic liquid composite material: adding ionic liquid into an organic solvent, and ultrasonically mixing uniformly for later use;
(3) preparing a graphite oxide powder/ionic liquid composite material modified electrode material: and ultrasonically and uniformly mixing the graphite oxide powder and the ionic liquid composite material according to the proportion of 0.2-0.6 g to 0.2-1 ml to prepare the modified electrode material.
2. The method for preparing the modified electrode material according to claim 1, wherein the ratio of the graphite powder to the mixed acid is as follows: 0.2-1 g: 1-3 ml; the ratio of the organic solvent to the ionic liquid is as follows: 0.2-4 g for 1-3 ml.
3. The preparation method of the modified electrode material according to claim 1, wherein the mixed acid is a mixed acid of nitric acid and sulfuric acid or a mixed acid of nitric acid and hydrochloric acid, wherein the hydrochloric acid concentration is 36-38%, the sulfuric acid concentration is 95-98%, the nitric acid concentration is 65-68%, and the ratio of nitric acid to hydrochloric acid/sulfuric acid is 2-6: 1-3.
4. The preparation method of the modified electrode material according to claim 1, wherein the graphite powder and the mixed acid are fully and uniformly mixed and then subjected to ultrasonic treatment to uniformly disperse the graphite powder and the mixed acid.
5. The method for preparing the modified electrode material of claim 1, wherein the organic solvent is any one or more of DMSO, methanol, acetonitrile and DMF.
6. The method for preparing the modified electrode material as claimed in claim 1, wherein the ionic liquid is a hexafluorophosphate ionic liquid.
7. A modified electrode material, which is prepared by the method for preparing a modified electrode material according to any one of claims 1 to 6.
8. Use of the modified electrode material of claim 6 in a modified electrode.
9. A preparation method of a modified electrode is characterized in that the modified electrode material as claimed in any one of claims 1 to 5 is coated on the electrode and dried to prepare the modified electrode.
10. The use of the graphite oxide powder/ionic liquid modified electrode of claim 9 as a vitamin detection electrode.
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