CN103472106B - Lead silicate solid electrode using silver as base material and preparation method thereof - Google Patents
Lead silicate solid electrode using silver as base material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lead silicate solid electrode using silver as base material and a preparation method thereof. The lead silicate solid electrode comprises a silver wire, lead silicate and a heat-shrinkable tube, wherein a lead silicate layer is electroplated on the lower surface of the silver wire in an in-situ mode; and a heat-shrinkable tube layer is coated on the middle part of the silver wire and the upper part of the coated lead silicate. The lead silicate solid electrode has the advantages of high mechanical strength, high toughness, high sensitivity, small size, quick detection response, low detection lower limit, long service life and the like, is matched with a solid reference electrode, and is suitable for performing on-line detection and long-term in-situ monitoring on the silicate ion content in seawater, inland water, culture water, underground water, spring water and chemical and chemical engineering water media.
Description
Technical field
The present invention relates to a kind of take silver as lead silicate solid electrode of base material and preparation method thereof.
Background technology
Silicate is the important dissolved constituent in the natural water bodies such as underground water, surface fresh water, seawater, salt lake saline, also be limiting nutrient component important in water environment, the distribution of dissolves silicon acid group, for water ecological environments such as understanding ocean, lake, rivers, micro-ecological environment is significant.
Summary of the invention
The object of this invention is to provide a kind of take silver as lead silicate solid electrode of base material and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
Be that the lead silicate solid electrode of base material comprises filamentary silver, lead silicate, heat-shrink tube with silver; Filamentary silver lower surface original position electroplates coated one deck lead silicate, with the coated one deck heat-shrink tube in coated Si lead plumbate top in the middle part of filamentary silver.
The preparation method's step taking silver as the lead silicate solid electrode of base material is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the filamentary silver of 5 to 15 centimetres cleans successively in acetone and diluted acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) ammonium bicarbonate, sodium bicarbonate or saleratus are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole;
3) take filamentary silver as working electrode, i.e. anode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, and immerse in solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 0.5V, scans 1 to 5 circulation, forms silver carbonate precipitation on filamentary silver surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.1 to 0.2 mole;
5) filamentary silver being coated with silver carbonate is immersed this solution 6 to 14 hours, the lead ion in the silver carbonate on filamentary silver surface and solution is reacted, form ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
6) sodium silicate or sodium metasilicate are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole;
7) filamentary silver being coated with ceruse is immersed this solution 6 to 14 hours, the silicate ion in the ceruse on filamentary silver surface and solution is reacted, form lead silicate precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
8) heat-shrink tube is coated on the part that filamentary silver middle and upper part does not have coated Si lead plumbate, namely obtains solid silicic acid lead electrode.
Described diluted acid to be concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
Solid silicic acid lead electrode compact structure provided by the invention, be easy to the integrated use with other electrode, and preparation method is easy.This solid silicic acid lead electrode is applicable to the concentration detecting silicate ion in the natural water areas such as ocean, lake, ocean current, and carry out long-term on-line monitoring to hydro-environmental change, the discharge and the production run that are also applicable to industrial enterprise carry out online observation.
accompanying drawing illustrates:
Fig. 1 is the structural representation based on silver/lead silicate solid reference electrode;
In figure: filamentary silver 1, lead silicate 2, heat-shrink tube 3.
Embodiment
Be that the lead silicate solid electrode of base material comprises filamentary silver 1, lead silicate 2, heat-shrink tube 3 with silver; Filamentary silver 1 lower surface original position electroplates coated one deck lead silicate 2, with the coated one deck heat-shrink tube 3 in coated Si lead plumbate 2 top in the middle part of filamentary silver 1.
Described filamentary silver 1 needs coated Si lead plumbate 2, and be only the length of 1 cm being used as detection one end, remainder is used as the conductor of signal transmission, without the need to coated.
Select filamentary silver 1 as base material, be because it has good conductivity and toughness, and lead silicate 2 has relatively high conductivity, its electrochemical properties is better than other silicate.This electrode is using filamentary silver 1 as base material, and lead silicate 2 is sensitive membrane, has taken into account two kinds of materials advantage separately.
Filamentary silver 1 one aspect is the base material of electrode, is also the conductor of response signal simultaneously.The lead silicate 2 be coated on filamentary silver 1 plays a part silicate ion sensitive membrane, and the silicate ion dissolved in water body can form response electromotive force, i.e. voltage-type response signal between contrast electrode and solid silicic acid lead electrode.
The preparation method's step taking silver as the lead silicate solid electrode of base material is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the filamentary silver 1 of 5 to 15 centimetres cleans successively in acetone and diluted acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water.
Described diluted acid to be concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
Wipe oil also can use other organic solvent, as gasoline.There is fine and close hard oxide film metal surface, and dilute acid pretreatment rear oxidation film is dissolved.When bubbling appears in filamentary silver 1 in diluted acid, show that oxide film is dissolved, should take out from diluted acid as early as possible and enter next procedure, in order to avoid surface be reoxidized.
2) ammonium bicarbonate, sodium bicarbonate or saleratus are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole.
Recommendation sodium bicarbonate.Avoid using sodium carbonate and sal tartari to be pH value in order to reduce solution, thus suppress to form silver hydroxide on filamentary silver surface.
3) with filamentary silver 1 for working electrode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, is connected on electrochemical workstation, and immersed by above-mentioned three electrodes in solution, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 0.5V, scans 1 to 5 circulation, forms silver carbonate precipitation on filamentary silver 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
Silver carbonate is unstable, sees that light easily decomposes, advises operating under darkroom or dark conditions; Advise, before electrochemical reaction, solution is cooled to 0 to 4 ° of C simultaneously.
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.1 to 0.2 mole;
5) filamentary silver 1 being coated with silver carbonate is immersed this solution 6 to 14 hours, the lead ion in the silver carbonate on filamentary silver 1 surface and solution is reacted, form ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
This step still need operate under darkroom or dark conditions; Advise solution to be cooled to 0 to 4 ° of C simultaneously, and soak at this temperature.
The character of this reaction belongs to displacement reaction, and the lead ion in ie in solution enters solid phase, and the silver ion in silver carbonate enters solution, and reaction result is that silver carbonate is replaced by ceruse.
6) sodium silicate or sodium metasilicate are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole;
The molecular formula of sodium silicate is Na
2siO
3, the molecular formula of sodium metasilicate is Na
4siO
4, it is the product that sodium silicate and caustic soda react under hydrothermal conditions:
Na
2SiO
3+2NaOH=Na
4SiO
4+H
2O
7) filamentary silver 1 being coated with ceruse is immersed this solution 6 to 14 hours, the silicate in the ceruse on filamentary silver 1 surface and solution or metasilicic acid radical ion are reacted, form lead silicate 2 and precipitate; React the cleaning of rear water, then blotted with paper handkerchief;
The character of this reaction also belongs to displacement reaction, and the silicate in ie in solution or metasilicic acid radical ion enter solid phase, and the carbanion in ceruse enters solution, and reaction result is that ceruse is replaced by lead silicate.
Na
2SiO
3+PbCO
3=PbSiO
3+ Na
2CO
3
Na
4SiO
4+ PbCO
3+H
2O= PbSiO
3+Na
2CO
3+2NaOH
No matter use sodium silicate or sodium metasilicate, ceruse is all replaced by lead silicate.The lead silicate 2 be coated on outside filamentary silver plays ion-sensitive membrane interaction, and as a kind of insoluble compound, it is responsive to dissolves silicon acid group concentration-response in aqueous medium, and the conductivity of lead silicate is relatively high, and response signal can be made to conduct to filamentary silver.
8) heat-shrink tube 3 is coated on the part that filamentary silver 1 middle and upper part does not have coated Si lead plumbate 2, namely obtains solid silicic acid lead electrode.
Heat-shrink tube 3 is the coated part not having lead silicate 2 only, plays insulation protection effect.
Embodiment 1:
1) be 0.5 millimeter by diameter, length is that the filamentary silver 1 of 10 centimetres cleans successively in acetone and watery hydrochloric acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) sodium bicarbonate is dissolved in the water, is mixed with the solution that concentration is 0.2 mole;
3) with filamentary silver 1 for working electrode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, is connected on electrochemical workstation, and immersed by above-mentioned three electrodes in sodium bicarbonate solution, adopt scan round potential method, sweep speed is 30Vs
-1, potential range 0 to 0.5V, scans 1 circulation, forms silver carbonate precipitation on filamentary silver 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.2 mole;
5) filamentary silver being coated with silver carbonate is immersed this solution 6 hours, the lead ion in the silver carbonate on filamentary silver 1 surface and solution is reacted, form ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
6) sodium silicate is dissolved in the water, is mixed with the solution that concentration is 0.2 mole;
7) filamentary silver being coated with ceruse is immersed this solution 6 hours, the metasilicic acid radical ion in the ceruse on filamentary silver surface and solution is reacted, form lead silicate 2 and precipitate; React the cleaning of rear water, then blotted with paper handkerchief;
8) heat-shrink tube 3 is coated on the part that filamentary silver 1 middle and upper part does not have coated Si lead plumbate 2, namely obtains solid silicic acid lead electrode.
Embodiment 2:
1) be 1 millimeter by diameter, length is that the filamentary silver 1 of 5 centimetres cleans successively in acetone and dilute sulfuric acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) saleratus is dissolved in the water, is mixed with the solution that concentration is 0.1 mole;
3) with filamentary silver 1 for working electrode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, is connected on electrochemical workstation, and immersed by above-mentioned three electrodes in sodium bicarbonate solution, adopt scan round potential method, sweep speed is 80Vs
-1, potential range 0 to 0.5V, scans 5 circulations, forms silver carbonate precipitation on filamentary silver 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.1 mole;
5) filamentary silver 1 being coated with silver carbonate is immersed this solution 14 hours, the lead ion in the silver carbonate on filamentary silver 1 surface and solution is reacted, form ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
6) sodium silicate is dissolved in the water, is mixed with the solution that concentration is 0.1 mole;
7) filamentary silver being coated with ceruse is immersed this solution 14 hours, the silicate ion in the ceruse on filamentary silver 1 surface and solution is reacted, form lead silicate 2 and precipitate; React the cleaning of rear water, then blotted with paper handkerchief;
8) heat-shrink tube 3 is coated on the part that filamentary silver 1 middle and upper part does not have coated Si lead plumbate 2, namely obtains solid silicic acid lead electrode.
Embodiment 3:
1) be 0.8 millimeter by diameter, length is that the filamentary silver 1 of 10 centimetres cleans successively in acetone and dilute sulfuric acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) by ammonium bicarbonate solubility in water, be mixed with the solution that concentration is 0.2 mole;
3) with filamentary silver 1 for working electrode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, is connected on electrochemical workstation, and immersed by above-mentioned three electrodes in sodium bicarbonate solution, adopt scan round potential method, sweep speed is 60Vs
-1, potential range 0 to 0.5V, scans 2 circulations, forms silver carbonate precipitation on filamentary silver 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.2 mole;
5) filamentary silver being coated with silver carbonate is immersed this solution 10 hours, the lead ion in the silver carbonate on filamentary silver 1 surface and solution is reacted, form ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
6) sodium silicate is dissolved in the water, is mixed with the solution that concentration is 0.2 mole;
7) filamentary silver 1 being coated with ceruse is immersed this solution 10 hours, the silicate ion in the ceruse on filamentary silver 1 surface and solution is reacted, form lead silicate 2 and precipitate; React the cleaning of rear water, then blotted with paper handkerchief;
8) heat-shrink tube 3 is coated on the part that filamentary silver 1 middle and upper part does not have coated Si lead plumbate 2, namely obtains solid silicic acid lead electrode.
Claims (2)
1. be a lead silicate solid electrode for base material with silver, it is characterized in that, its preparation process is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the filamentary silver (1) of 5 to 15 centimetres cleans successively in acetone and diluted acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) ammonium bicarbonate, sodium bicarbonate or saleratus are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole;
3) with filamentary silver (1) for working electrode, i.e. anode, graphite is solid reference electrode, and Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, and immersed by above-mentioned three electrodes in solution, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 0.5V, scans 1 to 5 circulation, forms silver carbonate precipitation on filamentary silver (1) surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) lead acetate is dissolved in the water, is mixed with the solution that concentration is 0.1 to 0.2 mole;
5) filamentary silver (1) being coated with silver carbonate is immersed this solution 6 to 14 hours, the lead ion in the silver carbonate on filamentary silver (1) surface and solution is reacted, forms ceruse precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
6) sodium silicate or sodium metasilicate are dissolved in the water, are mixed with the solution that concentration is 0.1 to 0.2 mole;
7) filamentary silver (1) being coated with ceruse is immersed this solution 6 to 14 hours, the silicate in the ceruse on filamentary silver surface and solution or metasilicic acid radical ion are reacted, form lead silicate (2) precipitation; React the cleaning of rear water, then blotted with paper handkerchief;
8) heat-shrink tube is coated on the part that filamentary silver (1) middle and upper part does not have coated Si lead plumbate (2), namely obtaining with silver is the lead silicate solid electrode of base material;
The lead silicate solid electrode of described with silver is base material comprises filamentary silver (1), lead silicate (2), heat-shrink tube (3); Filamentary silver (1) lower surface original position electroplates coated one deck lead silicate (2), filamentary silver (1) middle part and the coated one deck heat-shrink tube (3) in coated Si lead plumbate (2) top.
2. according to claim 1 a kind of take silver as the preparation method of the lead silicate solid electrode of base material, it is characterized in that, described diluted acid to be concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1912608A (en) * | 2006-08-21 | 2007-02-14 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method |
CN102156157A (en) * | 2011-01-10 | 2011-08-17 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
CN102445482A (en) * | 2011-11-09 | 2012-05-09 | 浙江大学 | Metal/nano metal based solid glucose electrode and its preparation method |
CN102507682A (en) * | 2011-10-27 | 2012-06-20 | 浙江大学 | Dissolved hydrogen sulfide detection electrode based on silver/nano silver and preparation method for dissolved hydrogen sulfide detection electrode |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4071427A (en) * | 1976-11-17 | 1978-01-31 | Curators Of The University Of Missouri | Arsenite electrode |
SU643792A1 (en) * | 1976-12-27 | 1979-01-25 | Тюменский индустриальный институт | Inversion-voltamperometric method of determining arsenate-ions in aqueous solutions |
JPS5550158A (en) * | 1978-10-05 | 1980-04-11 | Horiba Ltd | Cod measurement |
JPS5855747A (en) * | 1981-09-28 | 1983-04-02 | Horiba Ltd | Responsive membrane for nitric acid ion selective electrode and its preparation |
US4842698A (en) * | 1987-05-19 | 1989-06-27 | Canadian Patents And Development Limited/Societe Canadienne Des Brevets Et D'exploitation Limitee | Solid state arsenic probe for use in pyrometallurgical processes |
SU1659832A1 (en) * | 1989-01-06 | 1991-06-30 | Тюменский государственный университет | Method of determination of sulfite ions in aqueous media using inverse voltamperometry |
JPH02232557A (en) * | 1989-03-06 | 1990-09-14 | Nippon Ceramic Co Ltd | Co2 sensor |
US5002644A (en) * | 1989-10-30 | 1991-03-26 | Westinghouse Electric Corp. | Method for monitoring sulfates and chlorides at low concentration |
SU1711060A1 (en) * | 1990-02-15 | 1992-02-07 | Винницкий политехнический институт | Nitrate meter |
JP3186363B2 (en) * | 1993-08-05 | 2001-07-11 | 日本特殊陶業株式会社 | Ion electrode |
JP3154661B2 (en) * | 1996-06-13 | 2001-04-09 | 株式会社神戸製鋼所 | Low hydrogen coated arc welding rod |
CN1164936C (en) * | 2002-04-02 | 2004-09-01 | 浙江大学 | Metal/metal oxide pH electrode suitable for high temperature and high pressure use and its prepn |
CN1164937C (en) * | 2002-04-12 | 2004-09-01 | 浙江大学 | Electrochemical sensor of dissolved hydrogen sulfide in extreme exvironment |
JP2004239832A (en) * | 2003-02-07 | 2004-08-26 | Tdk Corp | Carbon dioxide sensor |
CN1229640C (en) * | 2003-08-25 | 2005-11-30 | 浙江大学 | Electrode for detecting dissolveld sulfate radical content in water body, its preparation and application method |
CN1226616C (en) * | 2004-01-14 | 2005-11-09 | 河北科技大学 | Selenium ion selective electrode |
JP4263117B2 (en) * | 2004-02-06 | 2009-05-13 | 新コスモス電機株式会社 | Carbon dioxide detector |
CN100371704C (en) * | 2005-01-14 | 2008-02-27 | 浙江大学 | Solid pH electrode pair and production thereof |
CN2938085Y (en) * | 2006-06-20 | 2007-08-22 | 梁光佳 | Fluorine ion selective electrode |
CN100458432C (en) * | 2006-06-27 | 2009-02-04 | 浙江大学 | Anti-interference metal/metal oxide pH electrode and preparation method |
CN101210902B (en) * | 2007-12-25 | 2012-05-23 | 福州大学 | Metal-metallic oxide pH electrode and method for making same |
CN101216446A (en) * | 2007-12-27 | 2008-07-09 | 上海神开石油化工装备股份有限公司 | Combined electrode for determining sulphur ion of drilling fluids |
CN101441193A (en) * | 2008-12-19 | 2009-05-27 | 西安建筑科技大学 | Nitrate radical ionic selectivity micro-electrode and preparing method thereof |
CN201352209Y (en) * | 2008-12-25 | 2009-11-25 | 西安建筑科技大学 | Ammonium ion selective combination microelectrode |
CN101858882B (en) * | 2010-03-17 | 2013-07-17 | 江南大学 | Preparation method of nitrate ion selective electrode based on polypyrrole film |
CN102288662B (en) * | 2011-05-11 | 2014-09-03 | 厦门大学 | Metal-metal oxide pH sensitive probe and preparation method thereof |
CN102539501A (en) * | 2011-11-15 | 2012-07-04 | 厦门大学 | Micro electrode for measuring potential of hydrogen (pH) in cells and preparation method thereof |
CN102706942B (en) * | 2012-02-08 | 2014-11-12 | 国网浙江杭州市萧山区供电公司 | Preparation method of sulfate ion selective membrane electrode |
CN103063724B (en) * | 2012-12-13 | 2014-12-10 | 浙江大学 | Solid carbonate ion electrode based on conductive polyaniline and preparing method thereof |
CN103063718B (en) * | 2012-12-13 | 2014-10-15 | 浙江大学 | Solid nitrate ion electrode based on conductive polyaniline and preparing method thereof |
CN103063721B (en) * | 2012-12-13 | 2014-10-15 | 浙江大学 | Solid nitrite ion electrode based on conductive polyaniline and preparing method thereof |
CN103196971A (en) * | 2013-03-28 | 2013-07-10 | 浙江大学 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
CN103293205B (en) * | 2013-06-08 | 2015-09-23 | 江南大学 | Based on the preparation method of all solid state ion-selective electrode of double membrane structure |
-
2013
- 2013-03-28 CN CN 201310104390 patent/CN103196971A/en not_active Withdrawn
- 2013-09-11 CN CN201310411530.0A patent/CN103472112B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310411433.1A patent/CN103472111B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310411531.5A patent/CN103472113B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310410930.XA patent/CN103472109B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310410956.4A patent/CN103472110B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310411468.5A patent/CN103472107B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310410948.XA patent/CN103472104B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310410950.7A patent/CN103472105B/en not_active Expired - Fee Related
- 2013-09-11 CN CN201310410960.0A patent/CN103472106B/en not_active Expired - Fee Related
- 2013-10-16 CN CN201310482283.3A patent/CN103698377B/en not_active Expired - Fee Related
- 2013-12-19 CN CN201310698042.2A patent/CN103698379B/en not_active Expired - Fee Related
- 2013-12-19 CN CN201310698146.3A patent/CN103675068B/en not_active Expired - Fee Related
-
2014
- 2014-01-16 CN CN201410019461.3A patent/CN103776880B/en not_active Expired - Fee Related
- 2014-01-16 CN CN201410019466.6A patent/CN103776885B/en not_active Expired - Fee Related
- 2014-02-10 CN CN201410046346.5A patent/CN103808780B/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1912608A (en) * | 2006-08-21 | 2007-02-14 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method |
CN102156157A (en) * | 2011-01-10 | 2011-08-17 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
CN102507682A (en) * | 2011-10-27 | 2012-06-20 | 浙江大学 | Dissolved hydrogen sulfide detection electrode based on silver/nano silver and preparation method for dissolved hydrogen sulfide detection electrode |
CN102445482A (en) * | 2011-11-09 | 2012-05-09 | 浙江大学 | Metal/nano metal based solid glucose electrode and its preparation method |
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CN103808780A (en) | 2014-05-21 |
CN103472105B (en) | 2015-08-12 |
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 |
CN103698377A (en) | 2014-04-02 |
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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