CN104007158B - The preparation method of complete solid-state integral type pH combined electrode device and electrode thereof - Google Patents
The preparation method of complete solid-state integral type pH combined electrode device and electrode thereof Download PDFInfo
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Abstract
The present invention relates to complete solid-state integral type pH combined electrode device and electrode preparation method thereof, comprise Ag/AgCl reference electrode, antimony electrode, copper conductor and insulating gum cover composition, antimony electrode is embedded in bottom the stainless steel hollow needle of reference electrode by insulating gum cover. Reference electrode is using stainless steel hollow needle as substrate, at its electroplating surface last layer silver, then carry out ultrasonic cleaning with deionized water, and then at its plated surface last layer AgCl, through washed with de-ionized water, finally with the perfluor sulfoacid resin solution being dissolved with supersaturation KCl, it is carried out coated; Antimony electrode, be common antimony electrode first in the sodium peroxide of melting oxidation form zone of oxidation film, and then with massfraction be 5%～10% perfluor sulfoacid resin solution antimony electrode is carried out coated, form hydrogen ion selective semi-permeable membranes. Combined electrode of the present invention has certain physical strength and puncture ability, it may be achieved to solid, semisolid, mashed prod, and the pH test of solution.
Description
Technical field
The present invention relates to the preparation field of electrochemical sensor, say the preparation method relating to a kind of complete solid-state integral type pH combined electrode device and electrode thereof more specifically, for realizing the solid to certain intensity, semisolid, mashed prod, and the pH test of solution.
Background technology
Traditional pH test macro is made up of reference electrode and the working electrode of two separation, it may also be useful to get up very inconvenient, and cannot realize the pH test of the solid to certain intensity, semisolid, mashed prod. Therefore there is one of the all-solid-state reference electrode of certain puncture ability and the pH combined electrode focus becoming Recent study of complete solid-state integral type.
Reference electrode, as the reference electrode measuring potential difference, common are hydrogen electrode, mercurous chloride electrode, and some are based on the reference electrode of difficulty soluble salt, such as Ag/AgCl reference electrode. The condition that hydrogen electrode realizes is harsher, seldom uses in test, and mercurous chloride electrode has certain danger owing to using when toxic substance mercury uses, Ag/AgCl reference electrode owing to cost is low, use safety, easily prepare, become the most common reference electrode. Traditional Ag/AgCl reference electrode mainly uses in water solution system, and needs often to change interior reference solution, it may also be useful to get up very inconvenient. Therefore Ag/AgCl all-solid-state reference electrode is one of main development trend of reference electrode. The research of Ag/AgCl all-solid-state reference electrode is mainly concentrated on three aspects: one is replace traditional interior reference solution with melting salt or the resin gel that is dissolved with salt, as shut out, precious medium people adopts urea-formaldehyde resin and the mixed gel of KCl powder, the people such as W.Vonau adopt the KCl of melting, but the response performance of electrode is unsatisfactory; Two is shaping with the powdered mixture direct pressing of Ag and AgCl, as number of patent application CN102368059A prepares the method for reference electrode with Ag/AgCl pressed powder, disclose the Ag/AgCl solid state reference electrode of the oblate cylinder that a kind of powder compressing machine is pressed into, but need to be kept in KCl solution, it may also be useful to inconvenient;Three is the dull and stereotyped reference electrode research of based thin film printing technology, such as number of patent application CN101915794A all-solid-state reference electrode and its preparation method, discloses a kind of dull and stereotyped type all-solid-state reference electrode based on thick film screen printing technology, but complex process.
At present, the research of pH electrode being had a lot, but the research of complete solid-state integral type pH combined electrode is also compared shortage, technology is also immature. Such as the antimony metal pH electrode preparation method that number of patent application CN102565164A duplicature is modified, disclose a kind of novel antimony electrode film modified through oxide film and perfluorinated sulfonic resin, substantially increase antimony electrode anti-interference performance and weather resistance, but do not relate to the making method of complete solid-state integral type compound pH electrode. And for example patent publication No. CN101236170A is based on the integrated all-solid-state pH electrochemical sensor of nanometer tungsten oxide and its preparation method, disclose a kind of integrated flat all-solid-state pH electrochemical sensor, but measuring accuracy is not high, time of response is longer, to the pH real-time testing bad adaptability of the solid of certain intensity, semisolid, mashed prod and solution.
Summary of the invention
The present invention is directed to current all-solid-state reference electrode complex manufacturing technology, response performance is general, the preparation method of a kind of complete solid-state integral type pH combined electrode device and electrode thereof is proposed, for the pH real-time testing of the solid to certain intensity, semisolid, mashed prod and solution.
The complete solid-state integral type pH combined electrode device of one of the present invention, comprise copper conductor, complete solid-state Ag/AgCl reference electrode, insulating gum cover and antimony electrode, described antimony electrode is embedded in the bottom of described complete solid-state Ag/AgCl reference electrode by described insulating gum cover, and described copper conductor is drawn from described complete solid-state Ag/AgCl reference electrode and described antimony electrode respectively.
In such scheme, described complete solid-state Ag/AgCl reference electrode is made up of stainless steel hollow needle, silver layer, silver chloride layer and perfluorinated sulfonic resin film from inside to outside successively.
In such scheme, described antimony electrode is made up of common antimony electrode, zone of oxidation film and hydrogen ion selective semi-permeable membranes from inside to outside successively.
In such scheme, described insulating gum cover is PVC insulating material, and the common antimony electrode that described copper conductor is fixed on described antimony electrode from described insulating gum cover top tapping is inner.
Described complete solid-state Ag/AgCl reference electrode preparation method, feature is: taking stainless steel hollow needle as substrate, silver layer, silver chloride layer on its plated surface successively, then carry out coated with the perfluor sulfoacid resin solution being dissolved with supersaturation KCl, forming perfluorinated sulfonic resin film, its preparation method's concrete steps are as follows:
(1) choose the stainless steel hollow needle of external diameter 5-8mm, length 80-100mm, carry out polishing grinding with 400 orders and 800 object sand paper successively, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(2) oil removing activation. By the stainless steel hollow needle through polishing grinding, it is placed in degreaser oil removal treatment 10-20 minute, then carries out ultrasonic cleaning with deionized water and flash baking in vacuum drying oven;
(3) nickel preplating. With the bottom 30-50mm surface preplating skim nickel of electrochemical plating at the hollow needle through activation treatment, and use deionized water ultrasonic cleaning, dry in vacuum drying oven;
(4) electrosilvering. 30-50mm bottom stainless steel hollow needle is carried out electrodeposition process, at its plated surface last layer argent, and carries out ultrasonic cleaning with deionized water, dry in vacuum drying oven;
(5) electrolytic chlorination.Silver-plated for stainless steel hollow needle part and platinum electrode are formed electrolytic system continuous current chlorinolysis 1-2 hour, obtains silver chloride coating, and carry out ultrasonic cleaning with deionized water, put into baking oven lucifuge and dry;
(6) resin-coated film. The KCl of supersaturation is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, this solution is coated in through chloridized stainless steel hollow needle bottom, repeatedly smear several time, then dry in 70-80 DEG C of vacuum drying oven;
(7) copper conductor is burn-on on the top of stainless steel hollow needle as lead-in wire.
The described antimony electrode preparation method through modifying, feature is: by common antimony electrode first oxidation formation zone of oxidation film in the sodium peroxide of melting, then with massfraction be 5%～10% perfluor sulfoacid resin solution antimony electrode is carried out coated, forming hydrogen ion selective semi-permeable membranes, its preparation method's concrete steps are as follows:
(1) high pure metal antimony powder is heated to molten state;
(2) metallic antimony of melting is injected specific mold, and one end of a copper conductor is rapidly inserted in mold, be cooled to room temperature, obtain the antimony electrode of front end in oval shape;
(3) by obtained antimony electrode, in the sodium peroxide of vertical insertion melting 5 minutes, the surface formation oxide film of antimony electrode, was cooled to room temperature, then by washed with de-ionized water and dry in vacuum drying oven;
(4) antimony electrode surface-coated massfraction after the oxidising treat-ment is 5%-10% perfluor sulfoacid resin solution, forms selectivity of hydrogen ion through film on its surface, dries in 70-80 DEG C of vacuum drying oven.
The useful effect that the present invention adopts above-mentioned technical solution to reach is:
(1) the present invention adopts the perfluor sulfoacid resin solution being dissolved with supersaturation KCl to be coated in Ag/AgCl reference electrode surface, prepare complete solid-state Ag/AgCl reference electrode, do not need the interior reference solution in traditional Ag/AgCl reference electrode and barrier film, avoid reference solution in often changing, it is convenient to preserve, and technique is simple, it may also be useful to convenient. (2) the present invention adopts the antimony electrode through modifying as working electrode, and immunity from interference improves greatly, weather resistance and better reliability. (3) the present invention adopts stainless steel hollow needle to prepare the pH combined electrode of complete solid-state integral type as substrate, preparation technology is simple, easy to use, the pH real-time testing of solution can not only be used for, and due to base material and working electrode material be all that metal object has very high physical strength, it is not easy in using to damage, also can show good adaptability for the solid of certain intensity with certain water content, semisolid, mashed prod.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, embodiment is described.
Fig. 1 is complete solid-state integral type pH combined electrode device composition structural representation.
Wherein, 1 is copper conductor; 2 is complete solid-state Ag/AgCl reference electrode; 3 is insulating gum cover; 4 is antimony electrode; 21 is stainless steel hollow needle; 22 is silver layer; 23 is silver chloride layer; 24 is perfluorinated sulfonic resin film (being dissolved with the KCl of supersaturation); 41 is common antimony electrode; 42 is zone of oxidation film; 43 is hydrogen ion selective semi-permeable membranes.
Embodiment
As shown in Figure 1, the complete solid-state integral type pH combined electrode device of one of the present invention, feature is: comprises copper conductor 1, complete solid-state Ag/AgCl reference electrode 2, insulating gum cover 3 and the antimony electrode 4 through modifying and forms;Copper conductor 1 is drawn from complete solid-state Ag/AgCl reference electrode 2 and antimony electrode 4 respectively; Antimony electrode 4 is embedded in bottom the stainless steel hollow needle 21 of complete solid-state Ag/AgCl reference electrode 2 by insulating gum cover 3.
Described insulating gum cover 3 is PVC insulating material, for connecting complete solid-state Ag/AgCl reference electrode 2 and the antimony electrode 4 through modifying, is positioned at bottom the stainless steel hollow needle 21 of reference electrode 2 by working electrode 4.
The complete solid-state integral type pH method for preparing composite electrode of one of the present invention, comprises complete solid-state Ag/AgCl reference electrode 2 preparation method and antimony electrode 4 preparation method two aspect through modifying.
Described complete solid-state Ag/AgCl reference electrode 2 preparation method, feature is: taking stainless steel hollow needle 21 as substrate, silver layer 22, silver chloride layer 23 on its plated surface successively, then carry out coated with the perfluor sulfoacid resin solution being dissolved with supersaturation KCl, forming perfluorinated sulfonic resin film 24, its preparation method's concrete steps are as follows:
(1) choose the stainless steel hollow needle 21 of external diameter 5-8mm, length 80-100mm, carry out polishing grinding with 400 orders and 800 object sand paper successively, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(2) oil removing activation. By the stainless steel hollow needle 21 through polishing grinding, it is placed in the degreaser of 40-70 DEG C oil removal treatment 10-20 minute, then carries out ultrasonic cleaning with deionized water and flash baking in vacuum drying oven. Wherein the formula of degreaser is: NaOH:40-60g/L, Na2CO3:15-25g/L, Na3PO4:20-40g/L, OP surfactant: 1-2g/L.
(3) nickel preplating. By bigger cathode current density in the mixing solutions of the HCl of NiCl2 and 50-150g/L of 180-200g/L, carry out anode electrolysis 1-2 minute, at the bottom 30-50mm surface preplating skim nickel of the hollow needle 21 through activation treatment, then use deionized water ultrasonic cleaning, and vacuum drying oven is dried;
(4) electrosilvering. 30-50mm bottom stainless steel hollow needle 21 is put into the K2CO3 mixing solutions of free KCN, 15-30g/L of KCN, 30-40g/L of 60-80g/L, cathode current density is 0.5-2A/dm2, galvanic deposit 3-5 minute, at its plated surface last layer argent 22, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
(5) electrolytic chlorination. By silver-plated for stainless steel hollow needle part 22 and platinum electrode composition electrolytic system continuous current chlorinolysis 1-2 hour in 0.1mol/LKCl solution, current density 1-2A/dm2, obtain silver chloride coating 23, then carry out ultrasonic cleaning with deionized water, and put into baking oven lucifuge and dry;
(6) resin-coated film. The KCl of supersaturation is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, this solution is coated in through chloridized stainless steel hollow needle 21 bottom, repeatedly smear several time, and dry in 70-80 DEG C of vacuum drying oven;
(7) copper conductor 1 is burn-on on the top of stainless steel hollow needle 21 as lead-in wire.
Described antimony electrode 4 preparation method through modifying, feature is: by common antimony electrode 41 first oxidation formation zone of oxidation film 42 in the sodium peroxide of melting, then with massfraction be 5%～10% perfluor sulfoacid resin solution antimony electrode is carried out coated, forming hydrogen ion selective semi-permeable membranes 43, its preparation method's concrete steps are as follows:
(1) high pure metal antimony powder is heated to molten state;
(2) metallic antimony of melting is injected specific mold, and one end (the other end is used as signal and exports) of a copper conductor is rapidly inserted in mold, be cooled to room temperature, obtain the common antimony electrode 41 of front end in oval shape;
(3) by obtained common antimony electrode 41, in the sodium peroxide of vertical insertion melting 5 minutes, the surface formation zone of oxidation film 42 of antimony electrode, was cooled to room temperature, then by washed with de-ionized water and dry in vacuum drying oven;
(4) antimony electrode surface-coated massfraction after the oxidising treat-ment is 5%-10% perfluor sulfoacid resin solution, forms hydrogen ion selective semi-permeable membranes 43 on its surface, dries in 70-80 DEG C of vacuum drying oven.
Respectively described electrode is carried out by several zwitterion, Oxidizing and Reducing Agents to the influence research of response performance by fixing interfering ion method, the selectivity coefficient K recordedijAll much smaller than 1, as shown in table 1, show common zwitterion (Na in the film modified complete solid-state integral type pH combined electrode of perfluorinated sulfonic resin is to soil+、K+、Ca2+、Cl-、Br-) there is good selectivity, and to oxidation, reduction ion [Fe (CN)6]3-、[Fe(CN)6]4-With citrate ion (C6H5O7 3-) also there is good selectivity, its reason is electronegative after perfluorinated sulfonic resin film ionization, it is possible to is interposed between outside film by interference negatively charged ion, avoids contacting with pH electrode, the immunity from interference of electrode, reliability are greatly improved.
Table 1
| Ion | Concentration/( mol·L-1) | Kij | Ion | Concentration/( mol·L-1) | Kij |
| Na+ | 1.0 | 2.6E-12 | NO3- | 1.0 | 2.10E-10 |
| K+ | 1.0 | 2.8E-12 | SO4 2- | 1.0 | 2.5 E-11 |
| Ca2+ | 1.0 | 3.0E-10 | [Fe(CN)6]3- | 0.1 | 4.2E-06 |
| Cl- | 1.0 | 1.6E-12 | [Fe(CN)6]4- | 0.1 | 5.1E-06 |
| Br- | 1.0 | 1.2E-10 | C6H5O7 3- | 0.1 | 3.5E-06 |
Claims (5)
1. a complete solid-state integral type pH combined electrode device, it is characterized in that, comprise copper conductor (1), complete solid-state Ag/AgCl reference electrode (2), insulating gum cover (3) and antimony electrode (4), described antimony electrode (4) is embedded in the bottom of described complete solid-state Ag/AgCl reference electrode (2) by described insulating gum cover (3), and described copper conductor (1) is drawn from described complete solid-state Ag/AgCl reference electrode (2) and described antimony electrode (4) respectively; Described complete solid-state Ag/AgCl reference electrode (2) obtains by the following method: A chooses the stainless steel hollow needle of external diameter 5-8mm, length 80-100mm, polishing grinding is carried out successively with 400 orders and 800 object sand paper, then carry out ultrasonic cleaning with deionized water, and dry in vacuum drying oven;
B oil removing activates: by the stainless steel hollow needle through polishing grinding, is placed in degreaser oil removal treatment 10-20 minute, then carries out ultrasonic cleaning with deionized water and flash baking in vacuum drying oven;
C nickel preplating: with the bottom 30-50mm surface preplating skim nickel of electrochemical plating at the hollow needle through activation treatment, and use deionized water ultrasonic cleaning, dry in vacuum drying oven;
D electrosilvering: 30-50mm bottom stainless steel hollow needle is carried out electrodeposition process, at its plated surface last layer argent, and carries out ultrasonic cleaning with deionized water, dries in vacuum drying oven;
E electrolytic chlorination: silver-plated for stainless steel hollow needle part and platinum electrode are formed electrolytic system continuous current chlorinolysis 1-2 hour, obtains silver chloride coating, and carry out ultrasonic cleaning with deionized water, puts into baking oven lucifuge and dries;
The resin-coated film of F: the KCl of supersaturation is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, this solution is coated in through chloridized stainless steel hollow needle bottom, repeatedly smear several time, then dry in 70-80 DEG C of vacuum drying oven;
G burn-ons a copper conductor as lead-in wire on the top of stainless steel hollow needle.
2. the complete solid-state integral type pH combined electrode device of one according to claim 1, it is characterized in that, described complete solid-state Ag/AgCl reference electrode (2) is made up of stainless steel hollow needle (21), silver layer (22), silver chloride layer (23) and perfluorinated sulfonic resin film (24) from inside to outside successively.
3. the complete solid-state integral type pH combined electrode device of one according to claim 1 and 2, it is characterized in that, described antimony electrode (4) is made up of common antimony electrode (41), zone of oxidation film (42) and hydrogen ion selective semi-permeable membranes (43) from inside to outside successively.
4. the complete solid-state integral type pH combined electrode device of one according to claim 3, it is characterized in that, described insulating gum cover (3) is PVC insulating material, and the common antimony electrode (41) that described copper conductor (1) is fixed on described antimony electrode (4) from described insulating gum cover (3) top tapping is inner.
5. a preparation method for complete solid-state Ag/AgCl reference electrode, comprises following steps:
A chooses the stainless steel hollow needle of external diameter 5-8mm, length 80-100mm, carries out polishing grinding with 400 orders and 800 object sand paper successively, then carries out ultrasonic cleaning with deionized water, and dries in vacuum drying oven;
B oil removing activates: by the stainless steel hollow needle through polishing grinding, is placed in degreaser oil removal treatment 10-20 minute, then carries out ultrasonic cleaning with deionized water and flash baking in vacuum drying oven;
C nickel preplating: with the bottom 30-50mm surface preplating skim nickel of electrochemical plating at the hollow needle through activation treatment, and use deionized water ultrasonic cleaning, dry in vacuum drying oven;
D electrosilvering: 30-50mm bottom stainless steel hollow needle is carried out electrodeposition process, at its plated surface last layer argent, and carries out ultrasonic cleaning with deionized water, dries in vacuum drying oven;
E electrolytic chlorination: silver-plated for stainless steel hollow needle part and platinum electrode are formed electrolytic system continuous current chlorinolysis 1-2 hour, obtains silver chloride coating, and carry out ultrasonic cleaning with deionized water, puts into baking oven lucifuge and dries;
The resin-coated film of F: the KCl of supersaturation is dissolved in the perfluor sulfoacid resin solution of massfraction 5%-10%, this solution is coated in through chloridized stainless steel hollow needle bottom, repeatedly smear several time, then dry in 70-80 DEG C of vacuum drying oven;
G burn-ons a copper conductor as lead-in wire on the top of stainless steel hollow needle.
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| CN105675682B (en) * | 2015-12-28 | 2019-03-26 | 中国人民大学 | A kind of nano wire microelectrode and the preparation method and application thereof that size is controllable |
| CN106018504B (en) * | 2016-05-09 | 2018-10-09 | 江苏大学 | A kind of pH detection double compensation methods of soil matrix cultivation multi-parameter compound sensor |
| CN106018516B (en) * | 2016-05-09 | 2018-08-21 | 江苏大学 | A kind of compound slab pH transducer production methods of graphene modified |
| CN106596682B (en) * | 2016-12-28 | 2019-03-19 | 上海应用技术大学 | A kind of hydrospace detection Go-Nafion composite membrane Ag/AgCl reference electrode and preparation method |
| CN108169302B (en) * | 2017-11-20 | 2020-05-12 | 深圳大学 | Three-electrode system and using method thereof |
| CN108828329A (en) * | 2018-04-27 | 2018-11-16 | 中国科学院地质与地球物理研究所 | A kind of ocean electric field measurement sensor and preparation method thereof |
| CN108562751A (en) * | 2018-05-04 | 2018-09-21 | 深圳市西尔曼科技有限公司 | The detection method of enzyme membrane and preparation method thereof, glycosylated hemoglobin |
| DE102018111336B4 (en) * | 2018-05-11 | 2021-09-30 | Stenon Gmbh | Devices and methods for in-situ soil analysis |
| CN109342520B (en) * | 2018-09-29 | 2019-10-18 | 中国科学院长春应用化学研究所 | A kind of all-solid-state pH combination electrode device and preparation method thereof |
| CN110514721B (en) | 2019-07-24 | 2021-08-03 | 江苏大学 | Self-water-storage and self-water-replenishing pH sensor |
| CN113406167B (en) * | 2021-06-29 | 2023-10-10 | 江苏大学 | Super-hydrophilic pH thick film sensor based on chemical corrosion method and preparation method |
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| US4575410A (en) * | 1982-03-11 | 1986-03-11 | Beckman Industrial Corporation | Solid state electrode system for measuring pH |
| CN2219497Y (en) * | 1994-05-12 | 1996-02-07 | 厦门大学 | Long-acting solid composite electrode |
| US5497091A (en) * | 1994-09-01 | 1996-03-05 | Applied Research Associates, Inc. | Surface mounted pH sensor for cone penetration testing |
| US7182847B1 (en) * | 2003-05-07 | 2007-02-27 | Millar Instruments | System and probe for monitoring pH levels of a sample medium |
| DE102006055221A1 (en) * | 2006-11-21 | 2008-05-29 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Electrode and combination electrode for the determination of electrochemical potentials |
| CN102565164B (en) * | 2012-02-01 | 2014-03-12 | 江苏大学 | Method for producing antimony pH electrode modified by two layers of films |
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