CN103196971A - Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate - Google Patents
Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate Download PDFInfo
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- CN103196971A CN103196971A CN 201310104390 CN201310104390A CN103196971A CN 103196971 A CN103196971 A CN 103196971A CN 201310104390 CN201310104390 CN 201310104390 CN 201310104390 A CN201310104390 A CN 201310104390A CN 103196971 A CN103196971 A CN 103196971A
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Abstract
The invention discloses a preparation method of a solid phosphate electrode based on aluminum and aluminum phosphate. The preparation method comprises the following steps of 1) placing an aluminum conductor sequentially in acetone and diluted acid for washing, and drying the aluminum conductor after being washed; 2) preparing a phosphoric acid solution; 3) immersing the aluminum conductor as a working electrode, graphite as a reference electrode and a platinum (Pt) sheet as an auxiliary electrode in the phosphoric acid solution, forming white aluminum phosphate precipitate on the surface of the aluminum conductor by utilizing a cycling scanning potential method, placing the aluminum conductor in alcohol, and then airing the aluminum conductor; 4) preparing a cation screened film solution by utilizing reagent of the Sigma company; 5) utilizing the aluminum conductor which is wrapped by the aluminum phosphate to rapidly dip into the cation screened film solution, and inverting the aluminum conductor for airing; and 6) utilizing a thermoplastic pipe to wrap the middle-upper part of the aluminum conductor, which is not wrapped by the aluminum phosphate or the cation screened film to obtain the solid phosphate electrode. The solid phosphate electrode prepared by the preparation method has the advantages of low cost, high mechanical strength, high sensitivity, small size, rapid detection response, minimal detection lower limit, long service life and the like.
Description
Technical field
The present invention relates to a kind of based on aluminium, the preparation method of the solid phosphoric acid root electrode of aluminum phosphate.
Background technology
Phosphoric acid and phosphate are food, chemical industry, the pharmaceutical raw materials of using always, also be important composition and the teleorganic nutrient of biosome, the increase of phosphate concentration in the water environment can cause the eutrophication of water body, stimulate prosperous of harmful algae, ecologic environment is worked the mischief.Phosphate concentration in the monitoring water body is one of main contents of ecological environmental protection, environment remediation.Phosphate radical exploring electrode commonly used at present belongs to the liquid film type electrode more, and volume is bigger, and is also comparatively fragile, is difficult to use the needs that carry out online observation and long term monitoring in actual environment.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art provides a kind of based on aluminium, the preparation method of the solid phosphoric acid root electrode of aluminum phosphate.
The objective of the invention is to be achieved through the following technical solutions:
Based on aluminium, preparation method's step of the solid phosphoric acid root electrode of aluminum phosphate is as follows:
1) with diameter be 0.5 to 1 millimeter, length is that 5 to 15 centimetres aluminum conductor (1) cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
2) phosphoric acid is dissolved in 5 to 10 times the alcohol, is mixed with phosphoric acid solution;
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 30 to 80mVs
-1, potential range 0 scans 5 to 10 minutes to 1V, forms aluminum phosphate (2) precipitation of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
4) with the following reagent of Sigma company, be dissolved in tetrahydrofuran or the N of 10 to 15 times of solute general assembly (TW)s, in the dinethylformamide, preparation kation screened film (3) solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2-2.5 %
2-nitrobenzene octyl ether 52-55 %
Polyvinylchloride 42-45 %
5) use the aluminum conductor (1) that is coated with aluminum phosphate (2) to dip in fast and get kation screened film (3) solution for preparing, be inverted then and dry;
6) thermoplastic tube (4) is coated on the part that aluminum conductor (1) middle and upper part does not coat aluminum phosphate (2) and kation screened film (3), namely obtains solid phosphoric acid root electrode.
Described alcohol is a kind of in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, the glycerine or several.
Described diluted acid is that concentration is a kind of in 5% to 15% hydrochloric acid, sulfuric acid, the nitric acid or several.
Solid phosphoric acid root electrode structure provided by the invention is small and exquisite, be easy to and the integrated use of other electrode, and the preparation method is easy.The kation screened film that the top layer coats makes it have good anti-interference.This solid phosphoric acid root electrode is applicable in natural waters such as ocean, lake, ocean current the concentration of surveying phosphate anion, water environment is changed carry out long-term on-line monitoring, is applicable to that also the discharging of industrial enterprise and production run carry out online observation.
Description of drawings:
Fig. 1 is based on aluminium, the structural representation of the solid phosphoric acid root electrode of aluminum phosphate;
Among the figure: aluminum conductor 1, aluminum phosphate 2, kation screened film 3, heat-shrink tube 4.
Embodiment
As shown in Figure 1, based on aluminium, the solid phosphoric acid root electrode of aluminum phosphate comprises aluminum conductor 1, aluminum phosphate 2, kation screened film 3, heat-shrink tube 4, aluminum conductor 1 lower surface original position is electroplated one deck aluminum phosphate 2, outside surface at aluminum phosphate 2 coats one deck kation screened film 3 again, and the part that aluminum conductor 1 middle and upper part does not coat aluminum phosphate 2 and kation screened film 3 is coated with thermoplastic tube 4.
Described aluminum conductor need coat aluminum phosphate and kation screened film, only is about 1 centimetre length as detection one end, and remainder need not to coat as the conductor that signal transmits.
Aluminum conductor is the base material of electrode on the one hand, also is the conductor of response signal simultaneously.The aluminum phosphate that is coated on the aluminum conductor plays a part the phosphate anion sensitive membrane.Its Response Mechanism is:
2AlPO
4?+?(PO
4)
3-?+?3H
2O?→?Al
2(HPO
4)
3?+?3OH
-
Al
2(HPO
4)
3?+?3(PO
4)
3-?+?9H
2O?→?2Al(H
2PO
4)
3?+?9OH
-
That is: aluminum phosphate has the trend of obtaining phosphate radical from environment, therefore can form response electromotive force, i.e. voltage-type response signal at electrode.
In addition, because the solubility product of aluminum phosphate is less than the phosphate of many bivalent cations, as Ca
2+, Sr
2+Deng, it can play displacement reaction with these bivalent cations, forms undesired signal.Outermost kation screened film plays the obstruct kation, but the effect that allows negative ion to pass through.
Based on aluminium, preparation method's step of the solid phosphoric acid root electrode of aluminum phosphate is as follows:
1) with diameter be 0.5 to 1 millimeter, length is that 5 to 15 centimetres aluminum conductor 1 cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
Remove greasy dirt and also can use other organic solvent, as gasoline.There is fine and close hard oxide film the metal surface, and it is dissolved that diluted acid is handled the rear oxidation film.When bubbling appears in diluted acid in aluminum conductor, show that oxide film is dissolved, should from diluted acid, take out and enter next procedure as early as possible, in order to avoid the surface is by oxidation again.
2) phosphoric acid is dissolved in 5 to 10 times the alcohol, is mixed with phosphoric acid solution;
Using alcohol as the solvent of phosphoric acid, is because reaction intermediate, the especially Al (H of aluminium and phosphoric acid
2PO
4)
3Soluble in water, but insoluble and pure, be that reaction medium can guarantee that intermediate product can be not dissolved with alcohol.
Described alcohol is a kind of in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, the glycerine or several.Because of isopropyl alcohol polarity height, the conductivity height, good with the phosphoric acid compatibility, therefore recommend to use isopropyl alcohol.
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 30 to 80mVs
-1, potential range 0 scans 5 to 10 minutes to 1V, forms aluminum phosphate 2 precipitations of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
Generally, aluminium and phosphatase reaction primary product are Al (H
2PO
4)
3In phosphoric acid-pure system, by the scan round of electric current, under the effect of extra electric field, be conducive to oxidation and the hydrionic reduction of aluminium, therefore suppressed intermediate product Al (H
2PO
4)
3And Al
2(HPO
4)
3Generation, AlPO in the galvanochemistry sediment
4Proportion is higher.
Alcohol-pickled purpose is to remove residual phosphoric acid and the alcohol of electrode surface.The employing room temperature is dried or vacuum drying is to change for fear of aluminum phosphate clad recurring structure in drying course, causes active the reduction.
4) with the following reagent of Sigma company, be dissolved in tetrahydrofuran (THF) or the N of 10 to 15 times of solute general assembly (TW)s, in the dinethylformamide (DMF), preparation kation screened film 3 solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2-2.5 %
2-nitrobenzene octyl ether 52-55 %
Polyvinylchloride 42-45 %
The dotriacontyl ammonio methacrylate belongs to quaternary ammonium compound, is commonly used for stabilizing agent, emulsifying agent, sanitizer, germifuge, antistatic agent.In prescription, can improve the water wettability of film, make water soluble anion be easy to see through.
2-nitrobenzene octyl ether is plastifier, softening agent and the kation impedance agent of using always.Its formed film can allow negative ion to pass through, but stops cation permeation, so it plays the cationic effect of shielding in prescription.
Polyvinylchloride is universal synthetic resin, plays the film forming agent effect in prescription, makes film have higher intensity and toughness.
Because solvent volatility is stronger, kation screened film solution should be now with the current, do not store.
5) use the aluminum conductor 1 that is coated with aluminum phosphate 2 to dip in fast and get kation screened film 3 solution that prepare, be inverted then and dry;
Use the kation screened film to coat the kation that can completely cut off in the water body, prevent they and the aluminum phosphate film formation undesired signal that reacts; In addition, avoid aluminum phosphate film and water body directly to contact the serviceable life that can prolong electrode greatly.
Inversion is dried and is conducive to unnecessary coating solution and trickles towards the rear portion along lead, avoids because the solution dump leaching makes film blocked up, is inverted response sensitivity and reduces.
6) thermoplastic tube 4 is coated on the part that aluminum conductor 1 middle and upper part does not coat aluminum phosphate 2 and kation screened film 3, namely obtains solid phosphoric acid root electrode.
Embodiment 1:
1) be 0.5 millimeter with diameter, length is that 10 centimetres aluminum conductor 1 cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
2) phosphoric acid is dissolved in 5 times the alcohol, is mixed with phosphoric acid solution;
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 50mVs
-1, potential range 0 scans 8 minutes to 1V, forms aluminum phosphate 2 precipitations of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
4) with the following reagent of Sigma company, be dissolved in the tetrahydrofuran (THF) of 10 times of solute general assembly (TW)s, preparation kation screened film 3 solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2.5 %
2-nitrobenzene octyl ether 55 %
Polyvinylchloride 42.5 %
5) use the aluminum conductor 1 that is coated with aluminum phosphate 2 to dip in fast and get kation screened film 3 solution that prepare, be inverted then and dry;
6) thermoplastic tube 4 is coated on the part that aluminum conductor 1 middle and upper part does not coat aluminum phosphate 2 and kation screened film 3, namely obtains solid phosphoric acid root electrode.
Embodiment 2:
1) be 1 millimeter with diameter, length is that 10 centimetres aluminum conductor 1 cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
2) phosphoric acid is dissolved in 8 times the alcohol, is mixed with phosphoric acid solution;
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 80mVs
-1, potential range 0 scans 5 minutes to 1V, forms aluminum phosphate 2 precipitations of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
4) with the following reagent of Sigma company, be dissolved in the N of 10 times of solute general assembly (TW)s, in the dinethylformamide (DMF), preparation kation screened film 3 solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2 %
2-nitrobenzene octyl ether 55 %
Polyvinylchloride 43 %
5) use the aluminum conductor 1 that is coated with aluminum phosphate 2 to dip in fast and get kation screened film 3 solution that prepare, be inverted then and dry;
6) thermoplastic tube 4 is coated on the part that aluminum conductor 1 middle and upper part does not coat aluminum phosphate 2 and kation screened film 3, namely obtains solid phosphoric acid root electrode.
Embodiment 3:
1) be 1 millimeter with diameter, length is that 10 centimetres aluminum conductor 1 cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
2) phosphoric acid is dissolved in 10 times the alcohol, is mixed with phosphoric acid solution;
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 30 mVs
-1, potential range 0 scans 10 minutes to 1V, forms aluminum phosphate 2 precipitations of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
4) with the following reagent of Sigma company, be dissolved in the N of 10 times of solute general assembly (TW)s, in the dinethylformamide (DMF), preparation kation screened film 3 solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2.5 %
2-nitrobenzene octyl ether 55 %
Polyvinylchloride 42.5 %
5) use the aluminum conductor 1 that is coated with aluminum phosphate 2 to dip in fast and get kation screened film 3 solution that prepare, be inverted then and dry;
6) thermoplastic tube 4 is coated on the part that aluminum conductor 1 middle and upper part does not coat aluminum phosphate 2 and kation screened film 3, namely obtains solid phosphoric acid root electrode.
Claims (3)
1. one kind based on aluminium, and the preparation method of the solid phosphoric acid root electrode of aluminum phosphate is characterized in that its step comprises as follows:
1) with diameter be 0.5 to 1 millimeter, length is that 5 to 15 centimetres aluminum conductor (1) cleans in acetone and diluted acid successively, to remove surface and oil contaminant and oxide film, again with dry after the washed with de-ionized water;
2) phosphoric acid is dissolved in 5 to 10 times the alcohol, is mixed with phosphoric acid solution;
3) with the aluminum conductor be working electrode, graphite is contrast electrode, and the Pt sheet is auxiliary electrode, is connected on the electrochemical workstation, and above-mentioned three electrodes are immersed in the phosphoric acid solution, adopts the scan round potential method, and sweep speed is 30 to 80mVs
-1, potential range 0 scans 5 to 10 minutes to 1V, forms aluminum phosphate (2) precipitation of white on the aluminum conductor surface; Earlier with alcohol-pickled, room temperature was dried or vacuum drying then after plating was finished;
4) with the following reagent of Sigma company, be dissolved in tetrahydrofuran or the N of 10 to 15 times of solute general assembly (TW)s, in the dinethylformamide, preparation kation screened film (3) solution, its composition is respectively by percentage to the quality:
Dotriacontyl ammonio methacrylate 2-2.5 %
2-nitrobenzene octyl ether 52-55 %
Polyvinylchloride 42-45 %
5) use the aluminum conductor (1) that is coated with aluminum phosphate (2) to dip in fast and get kation screened film (3) solution for preparing, be inverted then and dry;
6) thermoplastic tube (4) is coated on the part that aluminum conductor (1) middle and upper part does not coat aluminum phosphate (2) and kation screened film (3), namely obtains solid phosphoric acid root electrode.
2. according to claim 1 a kind of based on aluminium, the preparation method of the solid phosphoric acid root electrode of aluminum phosphate is characterized in that, described alcohol is a kind of in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, the glycerine or several.
3. according to claim 1 a kind of based on aluminium, the preparation method of the solid phosphoric acid root electrode of aluminum phosphate is characterized in that, described diluted acid is that concentration is a kind of in 5% to 15% hydrochloric acid, sulfuric acid, the nitric acid or several.
Priority Applications (16)
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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 |
CN201310410956.4A CN103472110B (en) | 2013-03-28 | 2013-09-11 | Arsenate solid electrode using metal wire as base material and preparation method thereof |
CN201310410948.XA CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
CN201310411531.5A 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 CN103472109B (en) | 2013-03-28 | 2013-09-11 | Arsenite solid electrode using metal wire as base material and preparation method thereof |
CN201310411530.0A 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 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 |
CN201310411468.5A CN103472107B (en) | 2013-03-28 | 2013-09-11 | A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof |
CN201310410950.7A 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 CN103472106B (en) | 2013-03-28 | 2013-09-11 | Lead silicate solid electrode using silver as base material and preparation method thereof |
CN201310482283.3A CN103698377B (en) | 2013-03-28 | 2013-10-16 | A kind of preparation method of metal/metal hydroxide pH electrode |
CN201310698042.2A 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 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 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 |
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CN201410046346.5A 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 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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CN 201310104390 Withdrawn CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
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 |
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 |
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 |
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 |
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 |
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 |
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 |
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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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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 |
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 |
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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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 |
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 |
CN201310410948.XA Expired - Fee Related CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
CN201310411468.5A Expired - Fee Related CN103472107B (en) | 2013-03-28 | 2013-09-11 | A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof |
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 |
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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 |
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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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CN103698379B (en) | 2015-08-12 |
CN103472109B (en) | 2015-06-17 |
CN103472104B (en) | 2015-06-17 |
CN103472109A (en) | 2013-12-25 |
CN103472107A (en) | 2013-12-25 |
CN103698377A (en) | 2014-04-02 |
CN103472113A (en) | 2013-12-25 |
CN103472111B (en) | 2015-06-17 |
CN103698377B (en) | 2016-05-18 |
CN103472111A (en) | 2013-12-25 |
CN103472104A (en) | 2013-12-25 |
CN103698379A (en) | 2014-04-02 |
CN103472106A (en) | 2013-12-25 |
CN103472107B (en) | 2015-08-12 |
CN103472105B (en) | 2015-08-12 |
CN103472106B (en) | 2015-02-25 |
CN103776880A (en) | 2014-05-07 |
CN103808780A (en) | 2014-05-21 |
CN103675068B (en) | 2015-10-21 |
CN103472110B (en) | 2015-06-17 |
CN103472112B (en) | 2015-08-12 |
CN103776885A (en) | 2014-05-07 |
CN103776885B (en) | 2015-12-09 |
CN103776880B (en) | 2015-10-21 |
CN103808780B (en) | 2015-11-04 |
CN103472112A (en) | 2013-12-25 |
CN103472105A (en) | 2013-12-25 |
CN103472110A (en) | 2013-12-25 |
CN103675068A (en) | 2014-03-26 |
CN103472113B (en) | 2015-08-12 |
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