CN100381811C - Method for fabricating electrode of Nano ceric oxide selective membrane - Google Patents
Method for fabricating electrode of Nano ceric oxide selective membrane Download PDFInfo
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- CN100381811C CN100381811C CNB2004100734764A CN200410073476A CN100381811C CN 100381811 C CN100381811 C CN 100381811C CN B2004100734764 A CNB2004100734764 A CN B2004100734764A CN 200410073476 A CN200410073476 A CN 200410073476A CN 100381811 C CN100381811 C CN 100381811C
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- ceric oxide
- nano ceric
- carboxymethyl cellulose
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Abstract
The present invention discloses a method for manufacturing a selective membrane electrode of nanometer cerium dioxide, which comprises two steps: (1) the preparation of the carboxymethyl cellulose thin film of the nanometer cerium dioxide; (2) the menufacture of the electrode. The manufactured selective membrane electrode of the nanometer cerium dioxide has the characteristics of low cost, quick response, high selectivity, high stability, high repeatability, etc.; the selective membrane electrode of the nanometer cerium dioxide can be widely used in electroanalytical chemistry.
Description
Technical field
The invention belongs to the electrode special in the Electroanalytical Chemistry, be applied to [Ce
4+]/[Ce
3+] the selectivity analyzing and testing that changes of ion concentration.
Background technology
Lot of experiments shows, under chemical reaction system is in away from EQUILIBRIUM CONDITION, because the effect of the various non-linear process in the reaction system, present extremely abundant dynamic behavior, usually the various space-time ordered structures of chemical reaction system are called the Nonequilibrium and Nonlinear Chemistry phenomenon, abbreviate the nonlinear chemical phenomenon as.Chemical oscillation is exactly wherein a kind of, be meant in some chemical reaction system, the concentration of certain several component or intermediate product in time, space and the phenomenon of generating period variation, in these phenomenons, elementary cell in the system (reaction molecular) has been subjected to unified order seemingly and oneself has organized concerted activities, thereby form the space-time order state of macroscopic view, so this class phenomenon also is self organization phenomenon or cooperative phenomenon.Oscillating reactions has complicated mechanism, and macro manifestations goes out the specific characteristic that abundant information much can be provided, and this field has caused more and more keen interest of people.The vibration chemical reaction has turned to applied research gradually from simple Research on Nonlinear Dynamics, as the applied research in analyzing and testing, biological chemistry, life science even meteorology and economics field.The foundation that chemical oscillating reaction is applied to analyzing and testing is that mainly test substance can produce interference to oscillating reactions.Some test substance can react with certain component in the oscillating reactions system, causes the change of this component concentration in reaction system, thereby causes the amplitude of oscillating reactions, the change of cycle or induction period.Amplitude, the change of cycle or induction period and the change of the concentration of test substance are certain linear, therefore we can be worth to determine the concentration of test substance by the change of amplitude, cycle or induction period, and have successfully set up the analyzing detecting method of materials such as heroin, morphine, ephedrine, p-dihydroxy-benzene.
In the research of carrying out the chemical oscillation phenomenon, generally be three-electrode system, mercurous chloride electrode is a contrast electrode, two metal platinum electrodes are respectively working electrode and to electrode.Platinum electrode is a universal electrode commonly used in the electrochemical gaging, but poor selectivity.In the chemical oscillation system, exist [Ce simultaneously
4+]/[Ce
3+] and [Br
-] two vibrations, these two vibrations can detect on the platinum working electrode, have only when two vibrations all are in highly stable state, and total vibration could be stablized, so it is longer generally to reach stable time, and the less stable of the system of mensuration.
Summary of the invention
In view of above-mentioned platinum electrode reaches shortcomings such as the steady state (SS) required time is long, stability is not enough at solution traditional chemical oscillation system, the object of the present invention is to provide a kind of method for making of electrode of Nano ceric oxide selective membrane.Promptly start with, seek one and only respond the electrodes selective that a kind of ion concentration changes from the selectivity of electrode.Through research and experiment for a long time, filtered out electrode of Nano ceric oxide selective membrane.This electrode is only to [Ce
4+]/[Ce
3+] swing and detect, so that system reaches easily is stable.
Purpose of the present invention can be achieved through the following technical solutions:
From production process, the method for making of electrode of Nano ceric oxide selective membrane is divided into the preparation of Nano ceric oxide selective membrane and two steps of electrode development finish.
1, raw material: nano cerium dioxide powder (self-control), carboxymethyl cellulose (analyzing pure), acetone (analyzing pure), φ 0.2～0.5mm platinum wire (99.999%);
2, instrument: ultrasonic cleaner (SK8200LH, Shanghai science ultrasonic instrument company limited produces), the beaker of 250mL, analytical balance (1/0,000 g), graduated cylinder (100mL), glass sheet (10 * 10cm);
3, method for making:
(1) preparation of nano ceric oxide carboxymethyl cellulose film: earlier the carboxymethyl cellulose of 0.1～0.4 gram is dissolved in 30～60 milliliters the acetone, the nano cerium dioxide powder that adds 0.01～0.04 gram, ultrasonic the mixing of strong retaining in ultrasonic cleaning machine, incline then and be applied on the cleaning glass sheet on the shelf that is fixed in the ultrasonic cleaning machine, under weak shelves ultrasound intensity, solution is uniformly dispersed.Along with the volatilization of solvent acetone, on glass sheet, formed the carboxymethyl cellulose film of nano ceric oxide, i.e. the cerium ion optional membrane.This film characterizes through atomic force microscope, and nano ceric oxide is evenly distributed in carboxymethyl cellulose, about 9～10 μ m of the thickness of film.The carboxymethyl cellulose film of prepared nano ceric oxide is water insoluble, dilute sulfuric acid, hydrochloric acid and aqueous slkali, but is easily destroyed by organic solvents such as acetone, chloroforms.
(2) electrode is made: in the electrode glass pipe, earlier nano ceric oxide carboxymethyl cellulose film is fixed in the lower end of glass tube with " brothers are good " glue, with 0.2～0.5mm platinum wire is internal reference electrode, and electrode passes the polycondensation formaldehyde materials and seals with the polycondensation formaldehyde materials, uses 0.01mol.L
-1～0.4mol.L
-1The cerous sulfate aqueous solution be interior reference solution, promptly make electrode of Nano ceric oxide selective membrane.
The beneficial effect of advantage of the present invention and generation is:
Made electrode of Nano ceric oxide selective membrane only responds a kind of variation of ion concentration, only to [Ce
4+]/[Ce
3+] vibrate and detect, having cheap, characteristics such as response is fast, electrode selectivity height, good stability, reappearance height, can be widely used in the Electroanalytical Chemistry.
In mensuration of the present invention, when adopting electrode of Nano ceric oxide selective membrane to make the work electrode, reach and stablize the needed time ratio platinum electrode electrode of working and reduced half.
Description of drawings
Fig. 1 is the block scheme that the present invention makes flow process
Fig. 2 is the atomic force microscope picture of nano ceric oxide carboxymethyl cellulose film
Fig. 3 is an electrode synoptic diagram of the present invention
Fig. 4 is to be the chemical oscillation figure of working electrode with the platinum electrode
Fig. 5 is that the present invention is the chemical oscillation figure of working electrode with the self-control electrodes selective
Fig. 6 is that the present invention is the stability of working electrode test system with the self-control electrodes selective
Fig. 7 is that the present invention is the reappearance of working electrode test system with the self-control electrodes selective
Fig. 8 is that the present invention is the influence of working electrode probe temperature to system with the self-control electrodes selective
Fig. 9 is that the present invention is that working electrode is tested the influence to system of acidity, concentration of component or relative scale with the self-control electrodes selective
Embodiment
In the Electroanalytical Chemistry, general with response time, stability, reappearance, temperature, acidity, concentration of component or relative scale evaluation index as electrodes selective.Below in conjunction with accompanying drawing technical scheme of the present invention is further described again.
Embodiment
By shown in Figure 1, making flow process of the present invention divided for two steps finished:
(1) preparation of nano ceric oxide carboxymethyl cellulose film: earlier the carboxymethyl cellulose of 0.2 gram is dissolved in 30 milliliters the acetone, the nano cerium dioxide powder that adds 0.02 gram, ultrasonic the mixing of strong retaining in ultrasonic cleaning machine, incline then and be applied on the cleaning glass sheet on the shelf that is fixed in the ultrasonic cleaning machine, under weak shelves ultrasound intensity, solution is uniformly dispersed.Along with the volatilization of solvent acetone, on glass sheet, formed the carboxymethyl cellulose film of nano ceric oxide, i.e. the cerium ion optional membrane.This film characterizes through atomic force microscope, and nano ceric oxide is evenly distributed in carboxymethyl cellulose, the about 10 μ m of the thickness of film.Learn that from test the carboxymethyl cellulose film of prepared nano ceric oxide is water insoluble, dilute sulfuric acid, hydrochloric acid and aqueous slkali, but is easily destroyed by organic solvents such as acetone, chloroforms.
Fig. 2 is the atomic force microscope picture of nano ceric oxide carboxymethyl cellulose film, as can be seen from Fig. 2, the about 20～25nm of the diameter of nano ceric oxide, it is comparatively even to distribute in carboxymethyl cellulose.
(2) electrode is made: press Fig. 3 machined electrode glass tube, earlier nano ceric oxide carboxymethyl cellulose film (4) is fixed in the lower end of glass tube with " brothers are good " glue, with 0.2～0.5mm platinum wire is internal reference electrode (1), electrode (1) passes the polycondensation formaldehyde materials and places in the glass tube, and seals (2) with the polycondensation formaldehyde materials.Use 0.01mol.L
-1～0.4mol.L
-1The cerous sulfate aqueous solution be interior reference solution (3), promptly make electrode of Nano ceric oxide selective membrane.
Comparative Examples
Make embodiment by oneself nano ceric oxide carboxymethyl cellulose film (4) and be fixed in the lower end of glass tube with " brothers are good " glue, be respectively working electrode with the platinum electrode and be the content that the working curve method of working electrode is measured Dopamine hydrochloride with the self-control electrodes selective.Fig. 4 is to be the chemical oscillation figure of working electrode with the platinum electrode, and Fig. 5 is that the present invention is the chemical oscillation figure of working electrode with the self-control electrodes selective.
From oscillating curve as can be seen, be working electrode with the platinum electrode, during 500s, system just begins to stablize; When adopting electrode of Nano ceric oxide selective membrane to make the work electrode, system tends towards stability at the very start, and reaches the stable time and obviously reduce, and the time that this has just shortened assay determination, has increased the test sample amount of unit interval, testing efficiency height.
Experimental example 1
As shown in Figure 6, under 30 ℃ condition, carry out in the mensuration of Dopamine hydrochloride, when adopting electrode of Nano ceric oxide selective membrane to make the work electrode, have the constant characteristics of amplitude size of oscillating curve, system is long stabilization time, can test for we provide a plurality of sample delivery points like this.
Experimental example 2
In the mensuration of carrying out Dopamine hydrochloride, when test adopted electrode of Nano ceric oxide selective membrane to make the work electrode, during elected majority difference sample introduction, system presented the reappearance (see figure 7).The reappearance of curve has improved the accuracy of assay determination, and simultaneously, after system was disturbed, the time that returns to virgin state had shortened, and can also repeat sample introduction, the time that this has just shortened assay determination, has increased the analytic sample number in the unit interval.
Experimental example 3
Change temperature.Fig. 8 is when adopting electrode of Nano ceric oxide selective membrane to make the work electrode in the time of 25 ℃, measure the oscillating curve of the content of Dopamine hydrochloride, Fig. 7 is the oscillating curve of the content of the mensuration Dopamine hydrochloride that the employing electrode of Nano ceric oxide selective membrane is made the work electrode under 30 ℃ condition, two figure compare, though change the oscillation period of system, other character is constant.Illustrate and adopt electrode of Nano ceric oxide selective membrane to make the work electrode, under constant temperature, its value is constant.
Experimental example 4
As can be seen from Figure 9: change acidity, concentration of component or the relative scale of oscillation system in certain scope, only cause the variation of determinand to disturbed value (variation in oscillation amplitude change, the cycle etc.) size of system, other characteristic is constant.
Claims (1)
1. the method for making of a nano ceric oxide electrodes selective is characterized in that two steps of branch finish:
(1) preparation of nano ceric oxide carboxymethyl cellulose film:
Earlier the carboxymethyl cellulose of 0.1～0.4 gram is dissolved in 30～60 milliliters the acetone, the nano cerium dioxide powder that adds 0.01～0.04 gram, ultrasonic the mixing of strong retaining in ultrasonic cleaning machine, incline then and be applied on the cleaning glass sheet on the shelf that is fixed in the ultrasonic cleaning machine, under weak shelves ultrasound intensity, solution is uniformly dispersed, volatilization along with solvent acetone, on glass sheet, formed the carboxymethyl cellulose film of nano ceric oxide, be the cerium ion optional membrane, the thickness of film is 9～10 μ m;
(2) electrode is made:
In the electrode glass pipe, earlier nano ceric oxide carboxymethyl cellulose film (4) is fixed in the lower end of glass tube with " brothers are good " glue, with 0.2～0.5mm platinum wire is internal reference electrode (1), electrode passes the polycondensation formaldehyde materials and places in the glass tube, and seal (2) with the polycondensation formaldehyde materials, use 0.01mo1.L
-1～0.4mo1.L
-1The cerous sulfate aqueous solution be interior reference solution (3), promptly make electrode of Nano ceric oxide selective membrane.
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|---|---|---|---|
| CNB2004100734764A CN100381811C (en) | 2004-12-20 | 2004-12-20 | Method for fabricating electrode of Nano ceric oxide selective membrane |
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| CNB2004100734764A CN100381811C (en) | 2004-12-20 | 2004-12-20 | Method for fabricating electrode of Nano ceric oxide selective membrane |
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| CN100381811C true CN100381811C (en) | 2008-04-16 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101726531B (en) * | 2009-12-16 | 2012-07-04 | 厦门大学 | Electrochemical detection method of dopamine in body fluid |
| CN103280339A (en) * | 2013-04-12 | 2013-09-04 | 上海大学 | Method for preparing cerium oxide electrode of supercapacitor |
| CN105116036A (en) * | 2015-08-13 | 2015-12-02 | 东北大学 | Preparation and usage method for cerium (IV) ion selectivity electrodes |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03120454A (en) * | 1989-10-03 | 1991-05-22 | Fuji Photo Film Co Ltd | Ion selective electrode |
| CN2127788Y (en) * | 1992-07-10 | 1993-03-03 | 大连市环境监测中心站 | Combined ion-selective electrode |
| CN1123913A (en) * | 1995-04-27 | 1996-06-05 | 山东大学 | Potassium ion selective electrode of phosphoric acid-oxygen-titanium-potassium monocrystal film |
| CN2603939Y (en) * | 2003-01-30 | 2004-02-18 | 古昆 | Ion-selective electrode for detecting methylpyrrolidine |
| US6768581B1 (en) * | 1998-11-30 | 2004-07-27 | Sola International Holdings Ltd. | Coated lens exhibiting substantially balanced reflectance |
-
2004
- 2004-12-20 CN CNB2004100734764A patent/CN100381811C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03120454A (en) * | 1989-10-03 | 1991-05-22 | Fuji Photo Film Co Ltd | Ion selective electrode |
| CN2127788Y (en) * | 1992-07-10 | 1993-03-03 | 大连市环境监测中心站 | Combined ion-selective electrode |
| CN1123913A (en) * | 1995-04-27 | 1996-06-05 | 山东大学 | Potassium ion selective electrode of phosphoric acid-oxygen-titanium-potassium monocrystal film |
| US6768581B1 (en) * | 1998-11-30 | 2004-07-27 | Sola International Holdings Ltd. | Coated lens exhibiting substantially balanced reflectance |
| CN2603939Y (en) * | 2003-01-30 | 2004-02-18 | 古昆 | Ion-selective electrode for detecting methylpyrrolidine |
Non-Patent Citations (1)
| Title |
|---|
| 改性壳聚糖膜用于醇水混合液分离的研究（2）-壳聚糖-羧甲基纤维素共混物膜. 张富尧，张一烽，沈之荃.高等化学学报，第15卷第7期. 1994 * |
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