CN106706736A - Method for improving stability of iridium/iridium oxide pH (potential of Hydrogen) electrode - Google Patents
Method for improving stability of iridium/iridium oxide pH (potential of Hydrogen) electrode Download PDFInfo
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- CN106706736A CN106706736A CN201611051235.9A CN201611051235A CN106706736A CN 106706736 A CN106706736 A CN 106706736A CN 201611051235 A CN201611051235 A CN 201611051235A CN 106706736 A CN106706736 A CN 106706736A
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- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
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Abstract
The invention discloses a method for improving the stability of an iridium/iridium oxide pH (potential of Hydrogen) electrode. The iridium/iridium oxide pH electrode is prepared through a cyclic thermal oxidation method; the heat preservation treatment is carried out on the electrode for 3h to 48h in a hydrothermal environment with a temperature of 100 to 250 DEG C and compactedness of 35 to 85 percent; the electrode subjected to the treatment has the advantages of being high in sensitivity, quick in response, good in repeatability, little in hysteresis, and the like. Problems of long hydration time, low efficiency, poor stability and the like existing in an iridium/iridium oxide electrode for a long term are effectively solved. An electrode improved through the method can be used at 25 to 150 DEG C, and has a wider usage temperature range.
Description
Technical field
The present invention relates to biosensor analysis technical field of measurement and test, more particularly to a kind of iridium/yttrium oxide pH electrode stabilities
Improved method.
Background technology
Used as the one kind in all solid-state electrode, metal oxide electrode is easy to make because of its good mechanical property, is lightly easy to
The features such as carrying, and it is wide concerned.Used as a member in platinum metal, metal iridium is gone back with its preferable chemical inertness by oxidation
The influence of originality ion is smaller, thus as most there is one of metal material of metal/metal oxide pH electrode of application prospect.
The common method for preparing iridium/yttrium oxide pH electrodes has electrochemical cyclic voltammetry, electrodeposition process, sputtering method and thermal oxidation method
Deng.Wherein, thermal oxidation method is with its preparation process is simple, low cost, is widely used the advantages of be easy to mass production.But heat
Electrode prepared by oxidizing process, its surface film oxide is dry film, and what is had soil shape crackle even occurs, and surface stress and defect are gold
Common phenomenon in category oxidation, thus, need to carry out prolonged hydration process in actual applications.Aquation causes that oxide is brilliant
There is regrowth in body, and be gradually reduced the influence brought by stress and defect, and the effect of electrode performance is improved so as to reach.Institute
Although being final step in electrode production process with aquation but while being also the crucial step of comparing for concerning electrode performance.Pass
The hydration process of system is that electrode is submerged in water at normal temperatures, but the method aquation cycle is relatively long, in a short time
Degree of hydration is insufficient, and electrode potential drift phenomenon is serious, and repeatedly test reappearance is poor, thus greatly limit it in reality
In application.
The content of the invention
It is an object of the invention to provide a kind of improved method of iridium/yttrium oxide pH electrode stabilities, the electrode electricity after improvement
Gesture drift phenomenon reduces, and electrode stability is substantially improved；The electrode is not only applicable in normal temperature pH tests, while certain
Stood good under the hot environment of scope.
Realizing the concrete technical scheme of the object of the invention is：
A kind of improved method of iridium/yttrium oxide pH electrode stabilities, the method includes step in detail below：
Step 1：By one section of 1 ~ 3cm iridium wires long, with sand papering light after, respectively in 1 ~ 3M HCl, acetone and ultra-pure water
It is cleaned by ultrasonic；Then, the iridium wire is immersed in 1 ~ 10M NaOH solutions and continuously boils 0.5 ~ 3h；2 ~ 5 DEG C in Muffle furnace/
Min temperature programmings are to 500 ~ 900 DEG C, the min of constant temperature 30；Repeat above-mentioned dip-coating-oxidizing process 2 ~ 3 times；Wherein one end is scraped off
The oxide-film of 1~2mm is about, platinum filament is welded, ohm current potential is drawn, and insulating resin is coated in weld, obtain iridium/yttrium oxide
PH electrodes；
Step 2：The iridium that step 1 is prepared/yttrium oxide pH electrodes are placed in the reactor of polytetrafluoroethyllining lining, thereto
Addition pure water, it is 30~80% to keep compactedness in reactor, by the hot 3~48h of hydration process of above-mentioned electrode water at 100~250 DEG C；
The iridium obtained after treatment/yttrium oxide pH electrodes, in the follow-on test of a wheat harvesting period, its fitting operations curve nearly all overlaps
Together, potential drift is fast with response in ± 5mv（<0.3s）, sensitivity is high（70.5±0.3mv/pH）, favorable reproducibility（13
It is secondary）, hysteresis quality it is small, stability feature high；Stabilization can be used in 25 ~ 150 DEG C of temperature ranges, and measurement sensitivity
（1.44 mv/T）With theoretical this paricular value of energy（1.39 mv/T）Compare identical.
Beneficial effects of the present invention：
The electrode that the present invention will circulate thermal oxide preparation accelerates electrode aquation by high-temperature water hot water method, makes electrode shorter
Time in reach certain degree of hydration, so as to improve drift electrode phenomenon, stabilized electrodes performance.Electricity after treatment
Pole is remarkably reinforced at aspects such as potential stability, reappearance and sensitivity, and potential drift phenomenon is also substantially improved, and is had
Improve to effect the problem of the potential drift that iridium/yttrium oxide pH exists for a long time.And, by the treated electricity of the present invention
Have preferable heat endurance, still conformed in the range of 25 ~ 150 DEG C can this spy's response, thus electrode after treatment can be with
Used within the scope of temperature wider.
Brief description of the drawings
Fig. 1 is the schematic diagram of iridium/yttrium oxide pH electrodes prepared by the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 4 process after electrode in standard pH buffer solutions, in 37 days reperformance test fitting work
Make curve map；
When m- potential curve figures of the Fig. 3 for the electrode after the treatment of the embodiment of the present invention 4 in standard pH buffer solutions；
Temperature-potential curve figures of the Fig. 4 for the electrode after the treatment of the embodiment of the present invention 4 under different test temperatures；
Fig. 5 be electrode after comparative example of the present invention treatment in standard pH buffer solutions, the work of reperformance test fitting in 37 days
Make curve map.
Specific embodiment
Embodiment 1
（1）By the one section long iridium wire of about 2cm, with sand papering light after, each ultrasound in 3M HCl, acetone and ultra-pure water respectively
30min is cleaned up.Then the iridium wire is immersed in 5M NaOH solutions and boils 1h.5 DEG C/min program the liters in Muffle furnace
Temperature is to 800 DEG C, the min of constant temperature 30.Repeat dip-coating-oxidizing process 2 times.Wherein one end is scraped off the oxide-film for being about 1~2mm, and
Welding platinum filament, draws ohm current potential, and coats insulating resin in weld, obtains iridium/yttrium oxide pH electrodes；Its structure such as Fig. 1
It is shown, in figure, yttrium oxide, 1；Metal iridium matrix 2；Platinum filament 3；Insulating coating 4；
（2）Will（1）In it is obtained be placed in polytetrafluoroethyllining lining to iridium/yttrium oxide pH electrodes, be added to ultrapure
Water, it is 50% to keep compactedness in reactor, by the electrode water hot water 12h at 100 DEG C, obtains the iridium/oxidation through processing
Iridium pH electrodes.
Embodiment 2
（1）By the one section long iridium wire of about 2cm, with sand papering light after, each ultrasound in 3M HCl, acetone and ultra-pure water respectively
30min is cleaned up.Then the iridium wire is immersed in 5M NaOH solutions and boils 1h.5 DEG C/min program the liters in Muffle furnace
Temperature is to 800 DEG C, the min of constant temperature 30.Repeat dip-coating-oxidizing process 2 times.Wherein one end is scraped off the oxide-film for being about 1~2mm, and
Welding platinum filament, draws ohm current potential, and coats insulating resin in weld, obtains iridium/yttrium oxide pH electrodes；
（2）Will（1）In it is obtained be placed in polytetrafluoroethyllining lining to iridium/yttrium oxide pH electrodes, be added to ultrapure
Water, it is 50% to keep compactedness in reactor, by the electrode water hot water 24h at 100 DEG C；Obtain the iridium/oxidation through processing
Iridium pH electrodes.
Embodiment 3
（1）By the one section long iridium wire of about 2cm, with sand papering light after, each ultrasound in 3M HCl, acetone and ultra-pure water respectively
30min is cleaned up.Then the iridium wire is immersed in 5M NaOH solutions and boils 1h.5 DEG C/min program the liters in Muffle furnace
Temperature is to 800 DEG C, the min of constant temperature 30.Repeat dip-coating-oxidizing process 2 times.Wherein one end is scraped off the oxide-film for being about 1~2mm, and
Welding platinum filament, draws ohm current potential, and coats insulating resin in weld, obtains iridium/yttrium oxide pH electrodes；
（2）Will（1）In obtained iridium/yttrium oxide pH electrodes be placed in polytetrafluoroethyllining lining, be added to ultra-pure water,
It is 80% to keep compactedness in reactor, by the electrode water hot water 12h at 220 DEG C；Obtain the iridium/yttrium oxide through processing
PH electrodes.
Embodiment 4
（1）By the one section long iridium wire of about 2cm, with sand papering light after, each ultrasound in 3M HCl, acetone and ultra-pure water respectively
30min is cleaned up.Then the iridium wire is immersed in 5M NaOH solutions and boils 1h.5 DEG C/min program the liters in Muffle furnace
Temperature is to 800 DEG C, the min of constant temperature 30.Repeat dip-coating-oxidizing process 2 times.Wherein one end is scraped off the oxide-film for being about 1~2mm, and
Welding platinum filament, draws ohm current potential, and coats insulating resin in weld, obtains iridium/yttrium oxide pH electrodes；
（2）Will（1）In obtained iridium/yttrium oxide pH electrodes be placed in polytetrafluoroethyllining lining, be added to ultra-pure water,
It is 80% to keep compactedness in reactor, by above-mentioned electrode water hot water 24h at 220 DEG C；Obtain the iridium/yttrium oxide through processing
PH electrodes.
Electrode after the present embodiment treatment delays in the standard that pH value is respectively 1.68,4.00,6.86,9.18,10.01 and 12.47
Rush in solution, the working curve diagram of reperformance test fitting in 37 days（Commercial saturation Ag/AgCl electrodes are reference electrode, data
Collection in every three days is once）, as shown in Figure 2；From figure 2 it can be seen that by obtaining electrode after hydro-thermal hydration process, its fitting side
Journey is E=- (70.5 ± 0.3) pH+ (800.5 ± 5), and Linear Quasi is right higher（R2⩾0.998）.The reperformance test work of 13 times
Curve is essentially coincided together, and potential drift is ± 5mv, has absolutely proved that the electrode stability after treatment is good, and reappearance is higher.
While its slope is also indicated that for 70.5 ± 0.3 mv/pH, the electrode of hydro-thermal hydration process has sensitivity higher.Therefore, should
Hydro-thermal hydration process method can not only be obviously improved electrode potential drift phenomenon, stabilized electrodes performance, and can also improve electrode
Sensitivity.
Electrode after the present embodiment treatment is respectively 1.68,4.00,6.86,9.18,10.01 and 12.47 mark in pH value
When m- potential curve figure in quasi- cushioning liquid（Commercial saturation Ag/AgCl electrodes are reference electrode, when being tested in each solution
Between be 5min, to ensure that potential reaches stable state）, as shown in Figure 3；From figure 3, it can be seen that either from 1.68,4.00,
6.86th, 9.18,10.01,12.47 successively gradually increase test solution pH value, or large span change test fluid pH value be from
It is directly switch in the solution of pH=1.68 in the buffer solution of pH=12.47, the electrode after treatment almost can make an immediate response（t<
3s）, electrode potential response is steady, and the hysteresis quality of electrode response during switch test between different pH is smaller, in large span
PH handoff procedures in, electrode can also keep being basically unchanged, and potential drift phenomenon almost disappears, invertibity higher in performance.
Electrode after the present embodiment treatment test temperature be respectively temperature at 25,50,80,100,120 and 150 DEG C-
Potential curve figure（The pH value of test solution is 7.00, and reference electrode is self-control Ag/AgCl reference electrodes）, as shown in Figure 4；From figure
The working curve table that the electrode after hydro-thermal hydration process is tested at 25,50,80,100,120 and 150 DEG C is can be seen that in 4
It is bright, treated electrode still keep can this spy response, fit equation is E=-1.44T+789.09.Its sensitivity（1.44）
This spy 1.39 compares identical with theoretical energy.Therefore, the electrode of hydro-thermal hydration process at least can in the range of 0 ~ 150 DEG C normal work
Make.
Comparative example
（1）By the one section long iridium wire of about 2cm, with sand papering light after, each ultrasound in 3M HCl, acetone and ultra-pure water respectively
30min is cleaned up.Then the iridium wire is immersed in 5M NaOH solutions and boils 1h.5 DEG C/min program the liters in Muffle furnace
Temperature is to 800 DEG C, the min of constant temperature 30.Repeat dip-coating-oxidizing process 2 times.Wherein one end is scraped off the oxide-film for being about 1~2mm, and
Welding platinum filament, draws ohm current potential, and coats insulating resin in weld, obtains iridium/yttrium oxide pH electrodes；
（2）Will（1）In obtained iridium/yttrium oxide pH electrodes be placed directly in normal temperature aquation 24h in ultra-pure water.
From figure 5 it can be seen that the electrode of normal temperature hydration process is in the test of a wheat harvesting period, electrode working curve compares
Discrete, than more serious, simply just there is the trend for gradually settling out the phase to electrode negative sense drift phenomenon after a test.At 37 days by a definite date
Continuity test in, the sensitivity of the electrode is maintained at 59 ± 1mv/pH, but potential but floats to 563 mv from 901,
Potential drift phenomenon is obvious.
Claims (1)
1. the improved method of a kind of iridium/yttrium oxide pH electrode stabilities, it is characterised in that：The method includes step in detail below：
Step 1：By one section of 1 ~ 3cm iridium wires long, with sand papering light after, respectively in 1 ~ 3M HCl, acetone and ultra-pure water
It is cleaned by ultrasonic；Then, the iridium wire is immersed in 1 ~ 10M NaOH solutions and continuously boils 0.5 ~ 3h；2 ~ 5 DEG C in Muffle furnace/
Min temperature programmings are to 500 ~ 900 DEG C, the min of constant temperature 30；Repeat above-mentioned dip-coating-oxidizing process 2 ~ 3 times；Wherein one end is scraped off
The oxide-film of 1~2mm is about, platinum filament is welded, ohm current potential is drawn, and insulating resin is coated in weld, obtain iridium/yttrium oxide
PH electrodes；
Step 2：The iridium that step 1 is prepared/yttrium oxide pH electrodes are placed in the reactor of polytetrafluoroethyllining lining, thereto
Addition pure water, it is 30~80% to keep compactedness in reactor, by the hot 3~48h of hydration process of above-mentioned electrode water at 100~250 DEG C；
Obtain improved iridium/yttrium oxide pH electrodes.
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| CN201611051235.9A CN106706736B (en) | 2016-11-25 | 2016-11-25 | A kind of improved method of iridium/yttrium oxide pH electrode stability |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109507253A (en) * | 2018-11-16 | 2019-03-22 | 郑州炜盛电子科技有限公司 | Yttrium oxide combination electrode and preparation method thereof and the pH sensor for using the electrode |
| CN110887879A (en) * | 2019-12-02 | 2020-03-17 | 华东师范大学 | Method for preparing iridium/iridium oxide pH electrode through supercritical treatment |
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2016
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109507253A (en) * | 2018-11-16 | 2019-03-22 | 郑州炜盛电子科技有限公司 | Yttrium oxide combination electrode and preparation method thereof and the pH sensor for using the electrode |
| CN110887879A (en) * | 2019-12-02 | 2020-03-17 | 华东师范大学 | Method for preparing iridium/iridium oxide pH electrode through supercritical treatment |
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