CN100371704C - Solid pH electrode pair and production thereof - Google Patents
Solid pH electrode pair and production thereof Download PDFInfo
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- CN100371704C CN100371704C CNB2005100489112A CN200510048911A CN100371704C CN 100371704 C CN100371704 C CN 100371704C CN B2005100489112 A CNB2005100489112 A CN B2005100489112A CN 200510048911 A CN200510048911 A CN 200510048911A CN 100371704 C CN100371704 C CN 100371704C
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Abstract
The present invention discloses a solid pH electrode and a making method thereof, which comprises a solid pH electrode and a reference electrode matched with the pH electrode, wherein the solid pH electrode uses active carbon powder in a reagent grade as raw material, and uses a proton sensitive compound to modify the carbon powder, and the solid pH electrode is made by compression moulding and surface coating. The reference electrode is composed of metallic silver wires, an active AgCl layer and a proton semipermeable membrane. The two detecting electrodes have the advantages of full-solid structure, small and fine size, firmness, durability, insensitivity to components of interference properties, favorable working performance under the conditions of wide temperature and pressure ranges, competence of long-term online monitoring in severe environment and suitability for online detection and long-term monitoring for chemistry, chemical industry, waste treatment, wastewater discharge and natural environment such as volcanoes, geothermy, etc.
Description
Technical field
The present invention relates to a kind of solid-state pH electrode pair and preparation method thereof.
Background technology
Acidity of Aikalinity is one of most important chemical property of aqueous solution.Many synthetic reactions in fields such as chemistry, chemical industry, medicine, materials, all directly relevant with Property of Acid and Alkali of Solution.In addition, Property of Acid and Alkali of Solution still is the important parameter of knowledge of natural environment environment and geologic function.Survey the pH value and can use current method, also can use potential method.Potential method pH sensor comprises glass electrode, the ion selectivity membrane electrode, and ion selective field effect transistor, etc.Yet it is too fragile that these electrodes have, as glass electrode and most of membrane electrode; The poor anti jamming capability that has, as metal/metal oxide type electrode, reductibility in the natural system and oxidisability ion all can cause interference to it; What also have is stable inadequately, has problems such as signal drift, needs constantly to demarcate.Ampere method sensor great majority have adopted the pH sensitive membrane, or plate the responsive enzyme of pH at electrode surface.In various degree there is not the similar problem of person in they yet.Online detection and long term monitoring field press for firm, and the all-solid-state pH electrode especially the sort ofly can be used for dirty environments, and as sewer, the electrode of blow-off pipe and high temperature and high pressure environment is as the down-hole observation in oil field and the long term monitoring of hydrothermal volcanic system.
Summary of the invention
The purpose of this invention is to provide a kind of solid-state pH electrode pair and preparation method thereof.
The solid-state pH electrode pair comprises a solid-state pH electrode and supporting with it contrast electrode, the solid-state pH electrode has tinsel, tinsel top layer one end is provided with insulating protective layer, the tinsel top layer other end is provided with the carbon dust layer that the proton sensitive compound is modified, and the carbon dust layer top layer of modifying at the proton sensitive compound is enclosed with the Nafion layer; Contrast electrode has filamentary silver, and filamentary silver top layer one end is provided with insulating protective layer, and the filamentary silver top layer other end is provided with the AgCl layer, is enclosed with the Nafion layer on AgCl layer top layer, and described proton sensitive compound is anthracene or 9,10-dibenzanthracene or phenanthrenequione.
The proton sensitive compound is an anthracene, English name Anthracene, molecular formula C
14H
109,10-dibenzanthracene, English name 9,10-diphenylanthracene, abbreviation DPA, molecular formula C
26H
18Phenanthrenequione, English name 9,10-Phenanthrenequinone, abbreviation PAQ, molecular formula C
14H
8O
2
Nafion is a kind of perfluor semi-annular jade pendant acid resin that E.I.Du Pont Company produces, and its chemical structural formula is as follows:
M=1 in the formula, 2 or 3; N=6 or 7; X is 900～1100.
The preparation method of solid-state pH electrode pair comprises the preparation method of solid-state pH electrode and the preparation method of contrast electrode.
The step of solid-state pH electrode preparation method is as follows:
1) in beaker, adds 1～3g reagent activated carbon powder, and 25～50mL contains 0.05～0.2molHCl and 0.05～0.2mol KCl solution, 10～20mL contains the acetone soln of 10～30mmol proton sensitive compound, solution is mixed, ultrasonic Treatment 5～10 minutes, continuous stirring 1～3 hour;
2) suction filtration, and use washed with de-ionized water, removing residual acid and salt, air dry or dry in 60～80 ℃ of baking ovens is stored in product in the closed container then;
3) get length 10～15cm, the tinsel of diameter 0.4～0.6mm is enclosed within the teflon heat-shrink tube on the tinsel, and 1cm left and right sides length is respectively reserved at two ends, use hair dryer or in baking oven, heat-shrink tube is heated to 330～350 ℃, make its contraction and be wrapped on the tinsel;
4) 10～20% cementing agent and step 2 product is evenly mixed, be filled in the mould, and tinsel is placed in material center, mould is placed on the oil press, open oil press and rise to 50～80 tons until pressure, release after 5～15 minutes is taken out the electrode of compression moulding from mould, grind off burr with quantitative filter paper;
5) dip in above-mentioned electrode and get the Nafion solution that concentration was 5～10% (by weight), take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 1～2 time the oven dry back in 60 °～80 ℃ baking ovens;
6) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 50～70 ℃ (2 ℃ of per minutes), constant temperature 1～2 hour rises to temperature 180～200 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 0.5～1.5 hour.
Contrast electrode preparation method's step is as follows:
7) 5～8g is analyzed pure AgCl powder and place crucible, heating is got length 10～15cm until the complete fusion of AgCl, the filamentary silver of diameter 0.4～0.6mm, the length of one end 5～8mm is immersed in the AgCl melt, take out after 2～3 seconds, treat melt cooling back repetition 2～3 times;
8) the teflon heat-shrink tube is enclosed within filamentary silver not by AgCl covering place, reserves 1cm left and right sides length for connection, use hair dryer or in baking oven, heat-shrink tube is heated to 330～350 ℃, make its contraction and be wrapped on the filamentary silver at the other end;
9) use the part that AgCl is arranged to dip in and get the Nafion solution that concentration was 5～10% (by weight), take out the back and be inverted,,, in 60 °～80 ℃ baking ovens, dry the back and repeat 1～2 time to keep coating film thickness even so that excessive solution is trickled towards the rear portion;
10) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 50～70 ℃ (2 ℃ of per minutes), constant temperature 1～2 hour rises to temperature 180～200 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 0.5～1.5 hour.
Said proton sensitive compound is a kind of in the following material:
Anthracene, English name Anthracene, molecular formula C
14H
10
9,10-dibenzanthracene, English name 9,10-diphenylanthracene, abbreviation DPA, molecular formula C
26H
18
Phenanthrenequione, English name 9,10-Phenanthrenequinone, abbreviation PAQ, molecular formula C
14H
8O
2
Said cementing agent is the ptfe emulsion that Jusheng Fluorine Chemistry Co Ltd, Zhejiang produces, and trade name is JF-4DC61 or JF-4DC62, and it contains 60% teflon, and all the other are moisture content and surfactant.
Said Nafion is a kind of perfluor semi-annular jade pendant acid resin that E.I.Du Pont Company produces, and its chemical structural formula is as follows:
M=1 in the formula, 2 or 3; N=6 or 7; X is 900～1100.
Advantage of the present invention is, pH electrode and supporting contrast electrode are structure of whole solid state, and volume is tiny, has very high physical strength and toughness, helps the miniaturization and the microminiaturization of detection instrument; The Nafion film that electrode surface plated has shielding action to the ion beyond the hydrogen ion, so it has good anti-interference in rugged surroundings, and signal stabilization; This combination of electrodes is suitable for making the in-situ chemical sensor, especially the sort ofly can be used for dirty environments, and as sewer, blow-off pipe and high temperature and high pressure environment are as the down-hole observation in oil field and the long term monitoring of hydrothermal volcanic system.
Description of drawings
Accompanying drawing is the structural representation of solid-state pH electrode pair; it comprises solid-state pH electrode and supporting with it contrast electrode; they are connected on the two poles of the earth of signal detecting and measuring apparatus (electric potential type sensor), among the figure: 1. tinsel 1, insulating protective layer 2,3. carbon dust layer 3,4.Nafion layer 4, filamentary silver 5, the AgCl layer 6 modified of proton sensitive compound.
Embodiment
As shown in drawings, it comprises a solid-state pH electrode and supporting with it contrast electrode the solid-state pH electrode pair, the solid-state pH electrode has tinsel 1, tinsel 1 top layer one end is provided with insulating protective layer 2, the tinsel 1 top layer other end is provided with the carbon dust layer 3 that the proton sensitive compound is modified, and carbon dust layer 3 top layer of modifying at the proton sensitive compound are enclosed with Nafion layer 4; Contrast electrode has filamentary silver 5, and filamentary silver 5 top layers one end is provided with insulating protective layer 2, and the filamentary silver 5 top layer other ends are provided with AgCl layer 6, are enclosed with Nafion layer 4 on AgCl layer 6 top layer, and described proton sensitive compound is anthracene or 9,10-dibenzanthracene or phenanthrenequione.
Solid-state pH electrode provided by the invention adopts the responding layer of the carbon dust of proton sensitive compound modified as the pH electrode.Carbon dust adopts the SILVER REAGENT active carbon powder, need meet the GB/T12496-1999 request of national standard, and the particle mean size of carbon dust should be below 2 microns.The proton sensitive compound is for analyzing pure or guaranteed reagent, is a kind of in the following material:
Anthracene, English name Anthracene, molecular formula C
14H
10
9,10-dibenzanthracene, English name 9,10-diphenylanthracene, abbreviation DPA, molecular formula C
26H
18
Phenanthrenequione, English name 9,10-Phenanthrenequinone, abbreviation PAQ, molecular formula C
14H
8O
2
They have chemistry, the dual reversibility of galvanochemistry, can following reversible reaction take place with proton and the electronics in the solution:
With the proton sensitive compound activated charcoal being repaired is a kind of physisorption reaction in essence, promptly is dissolved in the anthracene, 9 in the solution, and 10-dibenzanthracene and phenanthrenequione are by charcoal absorption.For making evenly mixed and promoting absorption, can use supersonic wave cleaning machine that the potpourri of activated charcoal and solution is vibrated.
Very stable through the activated charcoal of repairing, not seeing after the standing storage has the adsorption phenomena of taking off, but should keep in Dark Place in closed container, because anthracene, 9,10-dibenzanthracene and phenanthrenequione can be by the oxidations of airborne oxygen institute under illumination.
Tinsel in the electrode plays physical connection.For prolonging electrode life, preferably use spun gold.When paying the utmost attention to cost factor, also can use copper wire, avoid using filamentary silver.Using polytetrafluoroethylene (PTFE) heat-shrink tube clad metal silk is in order to form insulating protective layer, also can to substitute PTFE with fluorinated ethylene-propylene rare (FEP) heat-shrink tube.The FEP price is lower, but permanance and resistance to elevated temperatures are all not as PTFE.
The carbon dust mould compression molding that the proton sensitive compound is modified.For making electrode sturdy and durable, the employing ptfe emulsion is a cementing agent.The cementing agent consumption should be controlled at 12～16% of carbon dust weight, crosses low then pole strength and reduces, and too high then electric conductivity reduces.Should confirm during operation that tinsel is positioned at the central authorities of mould, start oil press and make pressure rise to 50～80 tons, powered-down, release after keep-uping pressure 5～15 minutes.The electrode of compression moulding can grind off the burr of electrode surface with the quantitative filter paper of drying.
At electrode surface plating Nafion film is anti-interference and permanance in order to improve it.Nafion is a kind of perfluor semi-annular jade pendant acid resin that E.I.Du Pont Company produces, have very stable chemical property and good heat-resisting quantity, can be widely used in the sensitive membrane of fuel cell and sensor, exploring electrode in the medium-term and long-term use of the hot environment that approaches 200 ℃.The Nafion film is a kind of flat crystal of shortrange order when forming, and changes long range ordered structure after thermal treatment into, thereby kation is formed selectivity, forms the cation selective semi-permeable diaphragm.This tunic can see through proton, but outside negative ion oxidation agent and reductive agent be blocked in, and has avoided their interference to the pH electrode, has also prolonged the serviceable life of electrode simultaneously greatly.
In natural water body, have many components harmful to the Ag/AgCl contrast electrode, can with the active membrane generation chemical reaction of electrode surface:
2AgCl＋CO
3 2-→Ag
2CO
3+2Cl
2- (4)
2AgCl+S
2-→Ag
2S+2Cl
2- (5)
Negative ion in the ie in solution and AgCl reaction generates the more salt of indissoluble, and product can cause the electrode signal drift, or causes the AgCl layer to peel off to make electrode failure.Plating Nafion film on contrast electrode, and form the negative ion screen layer by thermal treatment can cut off contacting of harmful constituent and electrode sensitive layer in the water body, thereby improves the stability of electrode, and prolongs its serviceable life.
According to energy Si Tedinglv, the potential difference (PD) between pH electrode and the contrast electrode is:
E
Actual measurement=E °-[(2.303RTm)/(nF)] pH (6)
E in the formula
Actual measurementBe the potential difference (PD) between pH electrode and the contrast electrode, under 25 ℃ of conditions, theoretical value is 59mV.E ° is the standard electric potential difference, and R is an equation of gas state constant, and T is a Kelvin temperature, and n and m are respectively electronics and the proton number that transfer takes place, and according to reaction equation (1)～(3), they are equal to 2.
Below in conjunction with embodiment the present invention is elaborated.
Example 1: the activated carbon powder that uses anthracene to modify prepares the solid-state pH electrode
1) add 2g reagent activated carbon powder in the beaker, and 20mL concentration is 5 moles hydrochloric acid, 30mL contains 7.4 solution that restrain KCl, add again 20mL contain 1.78 the gram anthracenes acetone soln, solution is mixed, ultrasonic Treatment 10 minutes, continuous stirring is 2 hours on the electromagnetic agitation instrument;
2) suction filtration, and use washed with de-ionized water, to remove residual acid and salt, in 60 ℃ of baking ovens, dry, then product is stored in the closed container;
3) get length 15cm, the copper wire of diameter 0.6mm is enclosed within the teflon heat-shrink tube on the copper wire, and 1cm length is respectively reserved at two ends, in baking oven heat-shrink tube is heated to 350 ℃, makes its contraction and is wrapped on the copper wire;
4) 0.24 gram JF-4DC61 ptfe emulsion and step 2 product is evenly mixed, be filled in the mould, and tinsel is placed in material center, mould is placed on the oil press, open oil press and rise to 60 tons until pressure, release after 10 minutes is taken out the electrode of compression moulding from mould, grind off burr with quantitative filter paper;
5) dip in above-mentioned electrode and get the Nafion solution that concentration was 5% (by weight), take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 2 times the oven dry back in 60 ℃ of baking ovens;
6) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 60 ℃ (2 ℃ of per minutes), constant temperature 2 hours rises to temperature 190 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 1 hour.
Example 2: use 9, the activated carbon powder that the 10-dibenzanthracene is modified prepares the solid-state pH electrode
1) add 1g reagent activated carbon powder in the beaker, and 10mL concentration is 5 moles hydrochloric acid, 15mL contains 3.7 solution that restrain KCl, add 10mL again and contain 1.7 grams 9, the acetone soln of 10-dibenzanthracene mixes solution, ultrasonic Treatment 5 minutes, continuous stirring is 1 hour on the electromagnetic agitation instrument;
2) suction filtration, and use washed with de-ionized water, to remove residual acid and salt, in 80 ℃ of baking ovens, dry, then product is stored in the closed container;
3) get length 10cm, the spun gold of diameter 0.4mm is enclosed within the teflon heat-shrink tube on the spun gold, and 1cm length is respectively reserved at two ends, in baking oven heat-shrink tube is heated to 340 ℃, makes its contraction and is wrapped on the spun gold;
4) 0.15 gram JF-4DC62 ptfe emulsion and step 2 product is evenly mixed, be filled in the mould, and tinsel is placed in material center, mould is placed on the oil press, open oil press and rise to 50 tons until pressure, release after 10 minutes is taken out the electrode of compression moulding from mould, grind off burr with quantitative filter paper;
5) dip in above-mentioned electrode and get the Nafion solution that concentration was 10% (by weight), take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 1 time the oven dry back in 80 ℃ of baking ovens;
6) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 70 ℃ (2 ℃ of per minutes), constant temperature 1 hour rises to temperature 200 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 1 hour.
Example 3: the activated carbon powder that uses phenanthrenequione to modify prepares the solid-state pH electrode
1) add 3g reagent activated carbon powder in the beaker, and 20mL concentration is 10 moles hydrochloric acid, 30mL contains 14 solution that restrain KCl, add again 20mL contain 6.24 the gram phenanthrenequione acetone soln, solution is mixed, ultrasonic Treatment 15 minutes, continuous stirring is 3 hours on the electromagnetic agitation instrument;
2) suction filtration, and use washed with de-ionized water, to remove residual acid and salt, in 60 ℃ of baking ovens, dry, then product is stored in the closed container;
3) get length 15cm, the copper wire of diameter 0.4mm is enclosed within the teflon heat-shrink tube on the copper wire, and 1cm length is respectively reserved at two ends, in baking oven heat-shrink tube is heated to 350 ℃, makes its contraction and is wrapped on the copper wire;
4) 0.36 gram JF-4DC61 emulsion and step 2 product is evenly mixed, be filled in the mould, and tinsel is placed in material center, mould is placed on the oil press, open oil press and rise to 60 tons until pressure, release after 15 minutes is taken out the electrode of compression moulding from mould, grind off burr with quantitative filter paper;
5) dip in above-mentioned electrode and get the Nafion solution that concentration was 5% (by weight), take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 2 times the oven dry back in 60 ℃ of baking ovens;
6) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 50 ℃ (2 ℃ of per minutes), constant temperature 2 hours rises to temperature 180 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 1 hour.
Example 4: prepare supporting contrast electrode
1) 6g is analyzed pure AgCl powder and place crucible, heating is got length 15cm until the complete fusion of AgCl, and the filamentary silver of diameter 0.6mm in the length immersion AgCl melt with the about 8mm of one end, takes out after 2 seconds, treats to repeat 3 times after the melt cooling;
2) the teflon heat-shrink tube is enclosed within filamentary silver not by AgCl covering place, reserves 1cm left and right sides length, in baking oven, heat-shrink tube is heated to 350 ℃, make its contraction and be wrapped on the filamentary silver at the other end;
3) use the part that AgCl is arranged to dip in and get the Nafion solution that concentration was 10% (by weight), take out the back and be inverted,,, in 60 ℃ of baking ovens, dry the back and repeat 2 times to keep coating film thickness even so that excessive solution is trickled towards the rear portion;
4) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 60 ℃ (2 ℃ of per minutes), constant temperature 2 hours rises to temperature 200 ℃ (about 3 ℃ of per minutes) again, constant temperature was slowly reduced to room temperature (0.4～0.6 ℃ of about per minute) with temperature after 1 hour.
Claims (5)
1. solid-state pH electrode pair, it is characterized in that, it comprises a solid-state pH electrode and supporting with it contrast electrode, the solid-state pH electrode has tinsel (1), tinsel (1) top layer one end is provided with insulating protective layer (2), tinsel (1) the top layer other end is provided with the carbon dust layer (3) that the proton sensitive compound is modified, and carbon dust layer (3) top layer of modifying at the proton sensitive compound is enclosed with Nafion layer (4); Contrast electrode has filamentary silver (5), and filamentary silver (5) top layer one end is provided with insulating protective layer (2), and filamentary silver (5) the top layer other end is provided with AgCl layer (6), is enclosed with Nafion layer (4) on AgCl layer (6) top layer, and said proton sensitive compound is an anthracene, molecular formula C
14H
10Or 9,10-dibenzanthracene, molecular formula C
26H
18Or phenanthrenequione, molecular formula C
14H
8O
2
2. a kind of solid-state pH electrode pair according to claim 1 is characterized in that said Nafion is a kind of perfluor semi-annular jade pendant acid resin, and its chemical structural formula is as follows:
M=1 in the formula, 2 or 3; N=6 or 7; X is 900～1100.
3. the preparation method of a solid-state pH electrode pair is characterized in that it comprises the preparation method of solid-state pH electrode and the preparation method of contrast electrode,
The step of solid-state pH electrode preparation method is as follows:
1) in beaker, adds 1～3g reagent activated carbon powder, and 25～50mL contains 0.05～0.2molHCl and 0.05～0.2mol KCl solution, 10～20mL contains the acetone soln of 10～30mmol proton sensitive compound, solution is mixed, ultrasonic Treatment 5～10 minutes, continuous stirring 1～3 hour;
2) suction filtration, and use washed with de-ionized water, removing residual acid and salt, air dry or dry in 60～80 ℃ of baking ovens is stored in product in the closed container then;
3) get length 10～15cm, the tinsel of diameter 0.4～0.6mm is enclosed within the teflon heat-shrink tube on the tinsel, and 1cm left and right sides length is respectively reserved at two ends, use hair dryer or in baking oven, heat-shrink tube is heated to 330～350 ℃, make its contraction and be wrapped on the tinsel;
4) 10～20% cementing agent and step 2 product is evenly mixed, be filled in the mould, and tinsel is placed in material center, mould is placed on the oil press, open oil press and rise to 50～80 tons until pressure, release after 5～15 minutes is taken out the electrode of compression moulding from mould, grind off burr with quantitative filter paper;
5) dip in above-mentioned electrode that to get concentration be 5～10% Nafion solution by weight, take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 1～2 time the oven dry back in 60 °～80 ℃ baking ovens;
6) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 50～70 ℃ by the speed of 2 ℃ of per minutes, constant temperature 1～2 hour rises to temperature 180～200 ℃ again, constant temperature cooled the temperature to room temperature after 0.5～1.5 hour; Contrast electrode preparation method's step is as follows:
7) 5～8g is analyzed pure AgCl powder and place crucible, heating is got length 10～15cm until the complete fusion of AgCl, the filamentary silver of diameter 0.4～0.6mm, the length of one end 5～8mm is immersed in the AgCl melt, take out after 2～3 seconds, treat melt cooling back repetition 2～3 times;
8) the teflon heat-shrink tube is enclosed within filamentary silver not by AgCl covering place, reserves 1cm left and right sides length for connection, use hair dryer or in baking oven, heat-shrink tube is heated to 330～350 ℃, make its contraction and be wrapped on the filamentary silver at the other end;
9) dip in the part that AgCl arranged that to get concentration be 5～10% Nafion solution by weight, take out the back and be inverted, so that excessive solution is trickled towards the rear portion, to keep coating film thickness even, repeat 1～2 time the oven dry back in 60 °～80 ℃ baking ovens;
10) electrode that is coated with the Nafion film is placed logical N
2Container in, temperature is risen to 50～70 ℃, constant temperature 1～2 hour rises to temperature 180～200 ℃ again, constant temperature cooled the temperature to room temperature after 0.5～1.5 hour, said proton sensitive compound is an anthracene, molecular formula C
14H
10Or 9,10-dibenzanthracene, molecular formula C
26H
18Or phenanthrenequione, molecular formula C
14H
8O
2
4. the preparation method of a kind of solid-state pH electrode pair according to claim 3 is characterized in that, said cementing agent is a ptfe emulsion, and it contains 60% teflon, and all the other are moisture content and surfactant.
5. the preparation method of a kind of solid-state pH electrode pair according to claim 3 is characterized in that, said Nafion is a kind of perfluor semi-annular jade pendant acid resin, and its chemical structural formula is as follows:
M=1 in the formula, 2 or 3; N=6 or 7; X is 900～1100.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5271820A (en) * | 1992-06-19 | 1993-12-21 | Monsanto Company | Solid state pH sensor |
| CN2153800Y (en) * | 1993-05-26 | 1994-01-19 | 黄启成 | Full solid state electronic ph electrode |
| CN1085837C (en) * | 1999-04-09 | 2002-05-29 | 清华大学 | Nanometer metal oxide solid pH electrode and prepn. method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5271820A (en) * | 1992-06-19 | 1993-12-21 | Monsanto Company | Solid state pH sensor |
| CN2153800Y (en) * | 1993-05-26 | 1994-01-19 | 黄启成 | Full solid state electronic ph electrode |
| CN1085837C (en) * | 1999-04-09 | 2002-05-29 | 清华大学 | Nanometer metal oxide solid pH electrode and prepn. method therefor |
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