CN103698377A - Preparation method of metal/metal hydroxide pH electrode - Google Patents
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Abstract
The invention discloses a preparation method of metal/metal hydroxide pH electrode. A hydroxide membrane is formed on the surface of inertia metal wire by electrochemical reaction, and the material is a metal wire with stable chemical property, such as Ti, Ta, Nb, Zr, Ir, W, Ru or Pd wire. The hydroxide membrane formed by electrochemical reaction has sensitive response to hydrogen ion concentration in aqueous medium, therefore the hydroxide membrane can be used as pH electrode. The electrode surface is covered with Nafion-H, which is a hydrogen ion semi-permeable membrane for protecting the sensitive membrane of electrode from being interfered by other components. According to the invention, metal hydroxide is used as an ion sensitive membrane of pH electrode, and compared with the oxide membrane, the hydroxide membrane has higher sensitivity and faster response time. The membrane material is synthesized by electrochemical reaction under normal temperature, and thickness and structure of the membrane can be controlled by adjusting parameters; the membrane material and the metal base material are firmly combined without peeling, therefore the product has longer usage life.
Description
Technical field
The present invention relates to a kind of preparation method of metal/metal oxyhydroxide pH electrode.
Background technology
Metal/metal oxyhydroxide and metal/metal oxide electrode are widely applied for surveying the pH value of aqueous medium, and it has, and volume is little, response is fast, steady performance.This type of electrode at present ion sputtering method or the high-temperature fusant methods of adopting is made more, and these two kinds of methods are all under hot conditions, make wire surface oxidized, and formed oxide is as the responsive film of hydrogen ion.Under hot conditions, obtaining oxidation film has the following disadvantages: the conditional parameter that is first preparation process is difficult to accurate control, and thickness and the structure of the oxide skin(coating) of formation are inhomogeneous, and the electrode interindividual variation of preparation is larger; Next is that tinsel and oxide skin(coating) shrinkage factor have marked difference in cooling procedure, between the two, easily peels off, and has a strong impact on the yield rate of making, and the serviceable life of electrode.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of metal/metal oxyhydroxide pH electrode is provided.
The preparation method's of metal/metal oxyhydroxide pH electrode step is as follows:
1) cut-off footpath is the tinsel of 0.1～0.8 millimeter, polish with schmigel in surface, to remove original oxidation film, then in acetone or triclene, boil, to remove organic impurities, then immerse hydrochloric acid or the salpeter solution that concentration is 3-6M, ultrasonic cleaning is more than 1 minute, after taking-up, with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 30 to 80m Vs
-1, sensitivity 10
-3a, using tinsel as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, above-mentioned three electrodes are immersed in aqueous slkali, scan 1 to 3 circulation, in wire surface, form precipitate metal hydroxides, after scanning, first wash with water, with anhydrous alcohol, clean again, in air, dry;
3) in one end wiry, scrape off one section of hydroxide layer, on this one end, burn-on copper wire or filamentary silver, as circuit and physical connection; After welding, on copper wire or filamentary silver, be coated heat-shrink tube, as insulation course;
4) with the tinsel that has been coated oxyhydroxide, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, even to be held in film thickness, in 60 ℃～80 ℃ baking ovens, dry, obtain metal/metal oxyhydroxide pH electrode.
Described material wiry is Ti, Ta, Nb, Zr, Ir, W, Ru or Pd.Described aqueous slkali is one or several in LiOH, NaOH, KOH solution, and its weight percent concentration is 5% to 10%.Described metal hydroxides is the oxyhydroxide of metal of the same race.
Described perfluorinated sulfonic resin chemical structural formula is as follows:
M=1 in formula, 2 or 3; N=6 or 7; X is 900 ~ 1100; Before using, with methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol, perfluorinated sulfonic resin is configured to saturated solution.
The present invention is usingd metal hydroxides as the ion sensitive membrane of pH electrode, compare with oxidation film there is higher sensitivity, response time faster.And membrane material synthesizes by electrochemical reaction at normal temperatures, can pass through thickness and the structure of the conditional parameter controlling diaphragms such as scanning voltage, sweep speed and scanning times; Membrane material is combined with metal base firmly, incrust, therefore has longer serviceable life.
accompanying drawing explanation:
Fig. 1 is the structural representation of the solid inferior sulfate radical electrode based on silver/silver sulfite;
In figure: tinsel 1, metal hydroxides film 2, hydrogen ion semi-permeable diaphragm 3, heat-shrink tube 4.
Embodiment
As shown in Figure 1, metal/metal oxyhydroxide pH electrode comprises tinsel 1, metal hydroxides 2, hydrogen ion semi-permeable diaphragm 3, heat-shrink tube 4; Tinsel 1 lower surface original position is electroplated layer of metal oxyhydroxide 2, and at the outside surface of metal hydroxides 2 coated one deck hydrogen ion semi-permeable diaphragm 3 again, the top of the middle part of tinsel 1 and hydrogen ion semi-permeable diaphragm 3 is coated with heat-shrink tube 4.
The present invention, by electrochemical reaction, forms oxyhydroxide 2 films on tinsel 1 surface, and the latter has sensitive response to the pH in aqueous medium, therefore can be used as pH electrode.
Material therefor is the tinsel of stable chemical nature, as Ti, and Ta, Nb, Zr, Ir, W, Ru and Pd silk.Length wiry can be determined according to the electrode size two aspect factors that need to and be easy to process, be generally 0.6～1.2 centimeter length.Ensureing under the prerequisite of required physical strength, select thinner tinsel to be conducive to reduce costs, and dwindle the size of electrode.The diameter of tinsel 1 generally should be between 0.1～0.5 millimeter.
The oxidation film of tinsel 1 surperficial self-assembling formation does not have electrochemical activity, can not be for the mensuration of pH value.Therefore, as the first step of making electrode, be, to remove the surperficial original oxidation film of tinsel 1.The method that can adopt mechanical grinding and chemical cleaning to combine.
Making another key of metal/metal oxyhydroxide pH electrode, is to want active hydroxide 2 films of tinsel 1 coated one deck in surface to hydrogen ion sensitivity.The present invention adopts electrochemical method to prepare the responsive film of hydrogen ion.
Regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 30 to 80m Vs
-1, sensitivity 10
-3a.Using tinsel 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 1 to 3 circulation, on tinsel 1 surface, forms metal hydroxides 2 precipitations.
Above method is to the model of electrochemical workstation and producer without specific (special) requirements, and scanning voltage, sweep speed and scanning times can flexible, generally speaking, scanning voltage is high, the film that scanning times multiform becomes is thicker, is conducive to increase the service life, but the corresponding reduction of response sensitivity.
In Electrochemical Scanning process, the reaction occurring on tinsel 1 belongs to redox reaction:
Me+nH
2O=Me(OH)n+n/2H
2
Me represents metallic element, and n is the quantivalency of this metal.Reaction result is that metal is oxidized, and the hydrogen in water is reduced.During reaction, alkali is reaction medium, and itself does not change.Described aqueous slkali is one or several in LiOH, NaOH, KOH solution, and its weight percent concentration is 5% to 10%.Recommendation LiOH, because its character is relatively gentle, and the ionic radius of Li is little, formed membrane aperture is also little, is conducive to improve the antijamming capability of film.
Because tinsel used 1 mostly is precious metal material, expensive, in its one end, the burn-on relatively inexpensive copper wire of a joint or filamentary silver are conducive to reduce costs as wire.If do not mind cost, can directly use the precious metal 1 of sufficient length.
After hydroxide film 2 forms, recommendation drying at room temperature, that is: washing, absolute ethyl alcohol clean, room temperature is dried, to avoid hyperthermia drying process membrane structure to change, and peeling off because of the inconsistent formation of shrinkage factor between film and base material in cooling procedure.
Using perfluorinated sulfonic resin to be coated electrode is in order to improve its anti-interference and serviceable life.The trade name of perfluorinated sulfonic resin is Nafion, is du pont company's product.Commodity have solution and two kinds of forms of pressed powder, and wherein pressed powder is used after need being mixed with saturated solution with methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol.Recommendation propyl alcohol or isopropyl alcohol are as the solvent of Nafion.After solvent evaporates, the film that Nafion forms only allows that hydrogen ion sees through, and other component can not see through, so it is a kind of hydrogen ion semi-permeable diaphragm, and sensitive membrane that can guard electrode is not disturbed by other component, and increases the service life.
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment 1: the making of titanium/titanium hydroxide pH electrode
1) cut-off footpath is the titanium silk 1 of 0.3 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1 centimetre length, in triclene, boil, take out titanium silk 1, in the hydrochloric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 30mVs
-1, sensitivity 10
-3a.Using titanium silk 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, by the LiOH solution of above-mentioned three electrodes immersion 5%, scans 1 circulation, on titanium silk 1 surface, forms titanium hydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of titanium silk 1, scrape off 2 layers of the titanium hydroxides of approximately 1 millimeters long.The diameter of burn-oning on this one end is the filamentary silver of 0.1 millimeter, as circuit and physical connection; After welding, on filamentary silver, be coated heat-shrink tube 4, as insulation course;
4) with the titanium silk 1 that has been coated titanium hydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 60 ℃ of baking ovens, dry, obtain titanium/titanium hydroxide pH electrode.
Embodiment 2: the making of zirconium/zirconium hydroxide pH electrode
1) cut-off footpath is the zirconium silk 1 of 0.8 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.5 centimetre lengths, in acetone, boil, take out zirconium silk 1, in the nitric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 80mVs
-1, sensitivity 10
-3a.Using zirconium silk 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on zirconium silk 1 surface, forms zirconium hydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of zirconium silk 1, scrape off 2 layers of one section of zirconium hydroxides.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the zirconium silk 1 that has been coated zirconium hydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 80 ℃ of baking ovens, dry, obtain zirconium/zirconium hydroxide pH electrode.
Embodiment 3: the making of tungsten/hydroxide tungsten pH electrode
1) cut-off footpath is the tungsten filament 1 of 0.5 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.2 centimetre lengths, in acetone, boil, take out tungsten filament 1, in the hydrochloric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 60mVs
-1, sensitivity 10
-3a.Using tungsten filament 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on tungsten filament 1 surface, forms hydroxide tungsten 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of tungsten filament 1, scrape off 2 layers of one section of zirconium hydroxides.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the tungsten filament 1 that has been coated hydroxide tungsten 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 70 ℃ of baking ovens, dry, obtain tungsten/hydroxide tungsten pH electrode.
Embodiment 4: the making of iridium/hydroxide iridium pH electrode
1) cut-off footpath is the iridium wire 1 of 0.6 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.2 centimetre lengths, in acetone, boil, take out iridium wire 1, in the hydrochloric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 60mVs
-1, sensitivity 10
-3a.Using iridium wire 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on iridium wire 1 surface, forms hydroxide iridium 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of iridium wire 1, scrape off 2 layers, one section of hydroxide iridium.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the iridium wire 1 that has been coated hydroxide iridium 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 70 ℃ of baking ovens, dry, obtain iridium/hydroxide iridium pH electrode.
Embodiment 5: the making of rhodium/rhodium hydroxide pH electrode
1) cut-off footpath is the rhodium silk 1 of 0.4 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.0 centimetre lengths, in acetone, boil, take out rhodium silk 1, in the hydrochloric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 80mVs
-1, sensitivity 10
-3a.Using rhodium silk 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on rhodium silk 1 surface, forms rhodium hydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of rhodium silk 1, scrape off 2 layers of one section of rhodium hydroxides.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the rhodium silk 1 that has been coated rhodium hydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 70 ℃ of baking ovens, dry, obtain rhodium/rhodium hydroxide pH electrode.
Embodiment 6: the making of palladium/palladium dydroxide pH electrode
1) cut-off footpath is the palladium silk 1 of 0.5 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.0 centimetre lengths, in acetone, boil, take out palladium silk 1, in the nitric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 60mVs
-1, sensitivity 10
-3a.Using palladium silk 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on palladium silk 1 surface, forms palladium dydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of palladium silk 1, scrape off one section of palladium dydroxide layer.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the palladium silk 1 that has been coated palladium dydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 70 ℃ of baking ovens, dry, obtain palladium/palladium dydroxide pH electrode.
Embodiment 7: the making of tantalum/tantalum hydroxide pH electrode
1) cut-off footpath is the tantalum wire 1 of 0.4 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1 centimetre length, in triclene, boil, take out tantalum wire 1, in the hydrochloric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 30mVs
-1, sensitivity 10
-3a.Using tantalum wire 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, by the LiOH solution of above-mentioned three electrodes immersion 5%, scans 1 circulation, on tantalum wire 1 surface, forms tantalum hydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of tantalum wire 1, scrape off 2 layers of the tantalum hydroxides of approximately 1 millimeters long.The diameter of burn-oning on this one end is the filamentary silver of 0.1 millimeter, as circuit and physical connection; After welding, on filamentary silver, be coated heat-shrink tube 4, as insulation course;
4) with the tantalum wire 1 that has been coated tantalum hydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 60 ℃ of baking ovens, dry, obtain tantalum/tantalum hydroxide pH electrode.
Embodiment 8: the making of niobium/niobium hydroxide pH electrode
1) cut-off footpath is the niobium silk 1 of 0.5 millimeter, after mechanical grinding is removed oxidation film, is cut into several sections of every section of approximately 1.2 centimetre lengths, in acetone, boil, take out niobium silk 1, in the nitric acid that is 3M in concentration after drying, ultrasonic cleaning is 2 minutes, then with distilled water, clean, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 80mVs
-1, sensitivity 10
-3a.Using niobium silk 1 as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, and above-mentioned three electrodes are immersed in aqueous slkali, scans 2 circulations, on niobium silk 1 surface, forms niobium hydroxide 2 precipitations.After scanning, first wash with water, then clean with anhydrous alcohol, in air, dry.
3) in one end of niobium silk 1, scrape off 2 layers of one section of niobium hydroxides.The copper wire of burn-oning on this one end, as circuit and physical connection; After welding, on copper wire, be coated heat-shrink tube 4, as insulation course;
4) with the niobium silk 1 that has been coated niobium hydroxide 2, dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming 3 even thickness, in 80 ℃ of baking ovens, dry, obtain niobium/niobium hydroxide pH electrode.
Claims (6)
1. a preparation method for metal/metal oxyhydroxide pH electrode, is characterized in that, its step is as follows:
1) cut-off footpath is 0.1～0.8 millimeter, length is the tinsel (1) of 5 to 15 centimetres, polish with schmigel in surface, to remove original oxidation film, then in acetone or triclene, boil, to remove organic impurities, immerse again hydrochloric acid or salpeter solution that concentration is 3-6M, ultrasonic cleaning more than 1 minute, is cleaned with distilled water after taking-up, air-dry;
2) regulate CHI760D electrochemical workstation, adopt cyclic voltammetry, scanning voltage 0-1.5V, sweep speed is 30 to 80m Vs
-1, sensitivity 10
-3a, using tinsel (1) as working electrode, platinum electrode is auxiliary electrode, and Ag/AgCl electrode is contrast electrode, is connected on electrochemical workstation, above-mentioned three electrodes are immersed in aqueous slkali, scan 1 to 3 circulation, on tinsel (1) surface, form metal hydroxides (2) precipitation, after scanning, first wash with water, with anhydrous alcohol, clean again, in air, dry;
3) in one end of tinsel (1), scrape off one section of oxyhydroxide (2) layer.
2. on this one end, burn-on copper wire or filamentary silver, as circuit and physical connection; After welding, on copper wire or filamentary silver, be coated heat-shrink tube, as insulation course;
4) with the tinsel (1) that has been coated oxyhydroxide (2), dip perfluorinated sulfonic resin saturated solution, after taking out, be inverted, so that unnecessary solution trickles towards rear portion, to keep film forming (3) even thickness, in 60 ℃～80 ℃ baking ovens, dry, obtain metal/metal oxyhydroxide pH electrode.
3. the preparation method of a kind of metal/metal oxyhydroxide pH electrode according to claim 1, is characterized in that, described material wiry is Ti, Ta, Nb, Zr, Ir, W, Ru or Pd.
4. the preparation method of a kind of metal/metal oxyhydroxide pH electrode according to claim 1, is characterized in that, described aqueous slkali is one or several in LiOH, NaOH, KOH solution, and its weight percent concentration is 5% to 10%.
5. the preparation method of a kind of metal/metal oxyhydroxide pH electrode according to claim 1, is characterized in that the oxyhydroxide that described metal hydroxides is metal of the same race.
6. the preparation method of a kind of metal/metal oxyhydroxide pH electrode according to claim 1, is characterized in that, described perfluorinated sulfonic resin chemical structural formula is as follows:
M=1 in formula, 2 or 3; N=6 or 7; X is 900 ~ 1100; Before using, with methyl alcohol, ethanol, propyl alcohol or isopropyl alcohol, perfluorinated sulfonic resin is configured to saturated solution.
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| CN 201310104390 CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
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| CN2013101043902 | 2013-03-28 | ||
| CN201310482283.3A CN103698377B (en) | 2013-03-28 | 2013-10-16 | A kind of preparation method of metal/metal hydroxide pH electrode |
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| CN 201310104390 Withdrawn CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| CN201310411530.0A Expired - Fee Related CN103472112B (en) | 2013-03-28 | 2013-09-11 | A kind of solid phosphoric acid root electrode based on silver/metal phosphate and preparation method thereof |
| CN201310411433.1A Expired - Fee Related CN103472111B (en) | 2013-03-28 | 2013-09-11 | Bismuth sulfide or antimony sulfide solid sulfur ion electrode using silver as base material and preparation method thereof |
| CN201310411531.5A Expired - Fee Related CN103472113B (en) | 2013-03-28 | 2013-09-11 | Based on the solid carbon acid group electrode and preparation method thereof of rare earth/rare earth carbonate |
| CN201310410930.XA Expired - Fee Related CN103472109B (en) | 2013-03-28 | 2013-09-11 | Arsenite solid electrode using metal wire as base material and preparation method thereof |
| CN201310410956.4A Expired - Fee Related CN103472110B (en) | 2013-03-28 | 2013-09-11 | Arsenate solid electrode using metal wire as base material and preparation method thereof |
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| CN201310410948.XA Expired - Fee Related CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
| CN201310410950.7A Expired - Fee Related CN103472105B (en) | 2013-03-28 | 2013-09-11 | Based on the solid carbon acid group electrode and preparation method thereof of metal/rare earth carbonate |
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| CN201310482283.3A Expired - Fee Related CN103698377B (en) | 2013-03-28 | 2013-10-16 | A kind of preparation method of metal/metal hydroxide pH electrode |
| CN201310698042.2A Expired - Fee Related CN103698379B (en) | 2013-03-28 | 2013-12-19 | A kind of solid ammonium ion electrode based on ammonium magnesium phosphate and preparation method thereof |
| CN201310698146.3A Expired - Fee Related CN103675068B (en) | 2013-03-28 | 2013-12-19 | A kind of solid nitric acid root electrode based on nitric acid oxidation bismuth and preparation method thereof |
| CN201410019461.3A Expired - Fee Related CN103776880B (en) | 2013-03-28 | 2014-01-16 | A kind of with titanium silk solid reference electrode that is base material and preparation method thereof |
| CN201410019466.6A Expired - Fee Related CN103776885B (en) | 2013-03-28 | 2014-01-16 | A kind of take tinsel as silicate electrode of base material and preparation method thereof |
| CN201410046346.5A Expired - Fee Related CN103808780B (en) | 2013-03-28 | 2014-02-10 | Based on the solid carbon acid group electrode and preparation method thereof of barium carbonate, strontium carbonate |
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| CN 201310104390 Withdrawn CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| CN201310411530.0A Expired - Fee Related CN103472112B (en) | 2013-03-28 | 2013-09-11 | A kind of solid phosphoric acid root electrode based on silver/metal phosphate and preparation method thereof |
| CN201310411433.1A Expired - Fee Related CN103472111B (en) | 2013-03-28 | 2013-09-11 | Bismuth sulfide or antimony sulfide solid sulfur ion electrode using silver as base material and preparation method thereof |
| CN201310411531.5A Expired - Fee Related CN103472113B (en) | 2013-03-28 | 2013-09-11 | Based on the solid carbon acid group electrode and preparation method thereof of rare earth/rare earth carbonate |
| CN201310410930.XA Expired - Fee Related CN103472109B (en) | 2013-03-28 | 2013-09-11 | Arsenite solid electrode using metal wire as base material and preparation method thereof |
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| CN201310410950.7A Expired - Fee Related CN103472105B (en) | 2013-03-28 | 2013-09-11 | Based on the solid carbon acid group electrode and preparation method thereof of metal/rare earth carbonate |
| CN201310410960.0A Expired - Fee Related CN103472106B (en) | 2013-03-28 | 2013-09-11 | Lead silicate solid electrode using silver as base material and preparation method thereof |
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| CN201310698042.2A Expired - Fee Related CN103698379B (en) | 2013-03-28 | 2013-12-19 | A kind of solid ammonium ion electrode based on ammonium magnesium phosphate and preparation method thereof |
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| CN201410019466.6A Expired - Fee Related CN103776885B (en) | 2013-03-28 | 2014-01-16 | A kind of take tinsel as silicate electrode of base material and preparation method thereof |
| CN201410046346.5A Expired - Fee Related CN103808780B (en) | 2013-03-28 | 2014-02-10 | Based on the solid carbon acid group electrode and preparation method thereof of barium carbonate, strontium carbonate |
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| CN107688045A (en) * | 2017-10-31 | 2018-02-13 | 南京航空航天大学 | A kind of electrochemistry pH sensors |
| CN107688045B (en) * | 2017-10-31 | 2019-03-22 | 南京航空航天大学 | A kind of electrochemistry pH sensor |
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| WO2022143315A1 (en) * | 2020-12-28 | 2022-07-07 | 浙江大学 | Metal iridium oxide electrode capable of quantitatively detecting ph in sulfur ion environment, preparation method therefor and use thereof |
| US11885762B2 (en) | 2020-12-28 | 2024-01-30 | Zhejiang University | Iridium/iridium oxide electrode for quantitatively detecting pH in sulfide ion environment, and preparation method and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103808780A (en) | 2014-05-21 |
| CN103472105B (en) | 2015-08-12 |
| CN103472106B (en) | 2015-02-25 |
| CN103472111B (en) | 2015-06-17 |
| CN103698379A (en) | 2014-04-02 |
| CN103472104A (en) | 2013-12-25 |
| CN103196971A (en) | 2013-07-10 |
| CN103472111A (en) | 2013-12-25 |
| CN103698377B (en) | 2016-05-18 |
| CN103472113A (en) | 2013-12-25 |
| CN103472110B (en) | 2015-06-17 |
| CN103675068B (en) | 2015-10-21 |
| CN103472107B (en) | 2015-08-12 |
| CN103472104B (en) | 2015-06-17 |
| CN103472113B (en) | 2015-08-12 |
| CN103776880A (en) | 2014-05-07 |
| CN103472105A (en) | 2013-12-25 |
| CN103776885B (en) | 2015-12-09 |
| CN103698379B (en) | 2015-08-12 |
| CN103472106A (en) | 2013-12-25 |
| CN103675068A (en) | 2014-03-26 |
| CN103472107A (en) | 2013-12-25 |
| CN103472109A (en) | 2013-12-25 |
| CN103472112A (en) | 2013-12-25 |
| CN103776880B (en) | 2015-10-21 |
| CN103472110A (en) | 2013-12-25 |
| CN103472109B (en) | 2015-06-17 |
| CN103808780B (en) | 2015-11-04 |
| CN103472112B (en) | 2015-08-12 |
| CN103776885A (en) | 2014-05-07 |
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