CN103472109B - Arsenite solid electrode using metal wire as base material and preparation method thereof - Google Patents
Arsenite solid electrode using metal wire as base material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an arsenite solid electrode using a metal wire as a base material and a preparation method thereof. The arsenite solid electrode comprises a metal wire, a metal arsenite, a cation shielding film and a heat-shrinkable tube, wherein a metal arsenite layer is electroplated on the lower surface of the metal wire in an in-situ mode; the cation shielding film is coated on the external surface of the metal arsenite; and the heat-shrinkable tube is coated on the middle part of the metal wire and the upper part of the cation shielding film. The arsenite 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 arsenite ion content in seawater, culture water and chemical and chemical engineering water media.
Description
Technical field
The present invention relates to a kind of take tinsel as arsenous anion solid electrode of base material and preparation method thereof.
Background technology
Arsenic is the modal chemical element of nature, and arsenous anion is the most important existence form of arsenic.At nature, arsenous anion can identify oneself to pollute, also can from natural pollution source, as the weathering containing arsenic geologic body, containing arsenic hydrothermal solution, hot spring and groundwater activities etc.To human health risk greatly, in detection water body, the content of arsenous anion is the important means that understanding arsenic pollutes distribution range, significant with improvement to environmental protection in arsenic pollution.
Summary of the invention
The object of this invention is to provide a kind of take tinsel as arsenous anion 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 arsenous anion solid electrode of base material comprises tinsel, arsenious acid metal, kation screened film, heat-shrink tube with tinsel, tinsel lower surface in-stiu coating one deck arsenious acid metal, at outside surface coated one deck kation screened film again of arsenious acid metal, the top of middle part wiry and kation screened film is coated with heat-shrink tube.
Described metal is Ag, Cu or Pb.
Described kation screened film is that it consists of by percentage to the quality: Polyvinylchloride 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
The step taking tinsel as the preparation method of the arsenous anion solid electrode of base material is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the tinsel 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) sodium arsenite or potassium arsenite are dissolved in the water, are mixed with sodium arsenite or potassium arsenite solution that concentration is 0.1 to 0.2 mol/L;
3) take tinsel as working electrode, i.e. anode, graphite is solid reference electrode, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, immerse in sodium arsenite or potassium arsenite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 1 to 10 circulation, forms arsenious acid precipitated metal in wire surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
5) dip the kation screened film solution/outstanding mixed liquid prepared with the wire portion being coated with arsenious acid metal fast, be then inverted and dry;
6) heat-shrink tube is coated on the top of middle part wiry and kation screened film, namely obtains arsenous anion solid electrode.
Described diluted acid to be mass percent concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
Metal in described arsenious acid metal is Ag, Cu or Pb.
Solid arsenous anion electrode structure provided by the invention is small and exquisite, be easy to the integrated use with other electrode, and preparation method is easy.This solid arsenous anion electrode is applicable to the concentration detecting arsenite 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 explanation
Fig. 1 is the structural representation of the arsenous anion solid electrode taking tinsel as base material;
In figure: tinsel 1, arsenious acid metal 2, kation screened film 3, heat-shrink tube 4.
Embodiment
Be that the arsenous anion solid electrode of base material comprises tinsel 1, arsenious acid metal 2, kation screened film 3, heat-shrink tube 4 with tinsel, tinsel 1 lower surface in-stiu coating one deck arsenious acid metal 2, at outside surface coated one deck kation screened film 3 again of arsenious acid metal 2, the middle part of tinsel 1 and the top of kation screened film 3 are coated with heat-shrink tube 4.
Described tinsel 1 needs the length be only as 1 cm detecting one end of coated arsenious acid metal 2 and kation screened film 3, and remainder is used as the conductor of signal transmission, without the need to coated.Described metal is the one in Ag, Cu, Pb, selects these tinsels 1 as base material, is because it has good conductivity and toughness.This electrode is using tinsel 1 as base material, and arsenious acid metal 2 is sensitive membrane, has structure simple, responds sensitive advantage.
Tinsel 1 one aspect is the base material of electrode, is also the conductor of response signal simultaneously.The arsenious acid metal 2 be coated on tinsel 1 plays a part arsenite ion sensitive membrane, and the arsenite ion dissolved in water body can form response electromotive force, i.e. voltage-type response signal between contrast electrode and solid arsenous anion electrode.Outermost kation screened film 3 plays a part guard electrode.
Described metal is Ag, Cu or Pb.
Described kation screened film is that it consists of by percentage to the quality: Polyvinylchloride 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.Wherein Polyvinylchloride is film forming agent; Tridodecylmethylammonium ammonium chloride belongs to quaternary ammonium compound, can improve the water wettability of film in formula, make water soluble anion be easy to through; Four (4-chlorphenyl) boric acid sylvite can allow negative ion to pass through, but stops cation permeable, and therefore it has the cationic effect of shielding in formula.Because solvent volatility is comparatively strong, kation screened film solution should be now with the current, do not store.
The step taking tinsel as the preparation method of the arsenous anion solid electrode of base material is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the tinsel 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) sodium arsenite or potassium arsenite are dissolved in the water, are mixed with sodium arsenite or potassium arsenite solution that concentration is 0.1 to 0.2 mol/L; Sodium arsenite or potassium arsenite can by the dioxygen oxidations in air, and solution should be now with the current, do not store.
3) with tinsel 1 for working electrode, i.e. anode, graphite is solid reference electrode, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, immerse in sodium arsenite or potassium arsenite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 1 to 10 circulation, forms arsenious acid metal 2 precipitate in wire surface; React the cleaning of rear water, then blotted with paper handkerchief; Answer gated sweep number of times, arsenious acid metal 2 is precipitated and is unlikely to blocked up.
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride (PVC) 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 0.6-1%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 87-90%.
5) dip the kation screened film 3 solution/outstanding mixed liquid prepared by tinsel 1 part being coated with arsenious acid metal 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the middle part of tinsel 1 and the top of kation screened film 3, namely obtains arsenous anion solid electrode.
Described diluted acid to be mass percent 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 tinsel 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.
Metal in described arsenious acid metal 2 is Ag, Cu or Pb.
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 arsenite is dissolved in the water, is mixed with the solution that concentration is 0.1 mol/L;
3) with filamentary silver 1 for working electrode (anode), graphite is solid reference electrode, and Pt sheet is auxiliary electrode (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 1V, scans 1 circulation, forms silver arsenite 2 precipitate on filamentary silver 1 surface, has reacted the cleaning of rear water, has then blotted with paper handkerchief;
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride (PVC) 8%, tridodecylmethylammonium ammonium chloride 2 %, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 1%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 89%;
5) dip the kation screened film 3 solution/outstanding mixed liquid prepared by filamentary silver 1 part being coated with silver arsenite 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the top of part and the kation screened film 3 not having silver arsenite 2 in the middle part of tinsel 1, namely obtains arsenous anion solid electrode.
Embodiment 2:
1) be 1 millimeter by diameter, length is that the copper wire 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) potassium arsenite is dissolved in the water, is mixed with the solution that concentration is 0.1 mol/L;
3) with copper wire 1 for working electrode (anode), graphite is contrast electrode, and Pt sheet is auxiliary electrode (negative electrode), is connected on electrochemical workstation, is immersed in potassium arsenite solution by above-mentioned three electrodes, and adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 10 circulations, forms copper arsenite 2 precipitate on copper wire 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride (PVC) 10%, tridodecylmethylammonium ammonium chloride 1 %, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 0.6%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 88.4%;
5) dip the kation screened film 3 solution/outstanding mixed liquid prepared by copper wire 1 part being coated with copper arsenite 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the top with kation screened film 3 in the middle part of tinsel 1, namely obtains arsenous anion solid electrode.
Embodiment 3:
1) be 1 millimeter by diameter, length is that the galvanized wire 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) sodium arsenite is dissolved in the water, is mixed with the solution that concentration is 0.2 mol/L;
3) with galvanized wire 1 for working electrode (anode), graphite is contrast electrode (negative electrode), and Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, be immersed in potassium arsenite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 2 circulations, forms lead arsenite 2 precipitate on galvanized wire 1 surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride (PVC) 9%, tridodecylmethylammonium ammonium chloride 1.6%, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 0.8%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 88.6%;
5) dip kation screened film 3 solution prepared by galvanized wire 1 part being coated with lead arsenite 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the top with kation screened film 3 in the middle part of tinsel 1, namely obtains arsenous anion solid electrode.
Claims (5)
1. one kind take tinsel as the arsenous anion solid electrode of base material, it is characterized in that it comprises tinsel (1), arsenious acid metal (2), kation screened film (3), heat-shrink tube (4), tinsel (1) lower surface in-stiu coating one deck arsenious acid metal (2), outside surface coated one deck kation screened film (3) again of arsenious acid metal (2), the middle part of tinsel (1) and the top of kation screened film (3) are coated with heat-shrink tube (4); Described kation screened film is that it consists of by percentage to the quality: Polyvinylchloride 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
2. according to claim 1 a kind of take tinsel as the arsenous anion solid electrode of base material, it is characterized in that, described metal is Ag, Cu or Pb.
3. be a preparation method for the arsenous anion solid electrode of base material with tinsel, it is characterized in that, its step is as follows:
1) diameter is 0.5 to 1 millimeter, length is that the tinsel (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) sodium arsenite or potassium arsenite are dissolved in the water, are mixed with sodium arsenite or potassium arsenite solution that concentration is 0.1 to 0.2 mol/L;
3) with tinsel (1) for working electrode, i.e. anode, graphite is solid reference electrode, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, immerse in sodium arsenite or potassium arsenite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 1 to 10 circulation, forms arsenious acid metal (2) precipitation in wire surface; React the cleaning of rear water, then blotted with paper handkerchief;
4) kation screened film solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: Polyvinylchloride 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%;
5) dip kation screened film (3) solution/outstanding mixed liquid prepared by tinsel (1) part being coated with arsenious acid metal (2) fast, be then inverted and dry;
6) heat-shrink tube (4) is coated on the middle part of tinsel (1) and the top of kation screened film (3), namely obtains arsenous anion solid electrode.
4. according to claim 3 a kind of take tinsel as the preparation method of the arsenous anion solid electrode of base material, it is characterized in that, described diluted acid to be mass percent concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
5. according to claim 3 a kind of take tinsel as the preparation method of the arsenous anion solid electrode of base material, it is characterized in that, the metal in described arsenious acid metal (2) is Ag, Cu or Pb.
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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 | ||
| CN201310410930.XA 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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| 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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| 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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| 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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| 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 |
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| 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 |
| 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 |
| 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 |
| 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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| CN112798669B (en) | 2020-12-28 | 2022-04-22 | 浙江大学 | Can be at S2-Metal iridium oxide electrode for quantitatively detecting pH value under environment and preparation method and application thereof |
Citations (5)
| 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 |
| CN1645124A (en) * | 2005-01-14 | 2005-07-27 | 浙江大学 | Solid pH electrode pair and production thereof |
| CN1869675A (en) * | 2006-06-27 | 2006-11-29 | 浙江大学 | Anti-interference metal/metal oxide pH electrode and preparation method |
| CN2938085Y (en) * | 2006-06-20 | 2007-08-22 | 梁光佳 | Fluorine ion selective electrode |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN100454012C (en) * | 2006-08-21 | 2009-01-21 | 浙江大学 | Pressure adaptive dissolving carbon dioxide exploring 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 |
| CN102156157B (en) * | 2011-01-10 | 2013-06-05 | 浙江大学 | All-solid-state carbonate ion selective electrode and manufacture method of all-solid-state carbonate ion selective electrode |
| CN102288662B (en) * | 2011-05-11 | 2014-09-03 | 厦门大学 | Metal-metal oxide pH sensitive probe and preparation method thereof |
| CN102507682B (en) * | 2011-10-27 | 2013-09-18 | 浙江大学 | Dissolved hydrogen sulfide detection electrode based on silver/nano silver and preparation method for dissolved hydrogen sulfide detection electrode |
| CN102445482B (en) * | 2011-11-09 | 2013-06-26 | 浙江大学 | Metal/nano metal based solid glucose electrode and its preparation method |
| 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
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- 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
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- 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 (5)
| 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 |
| CN1645124A (en) * | 2005-01-14 | 2005-07-27 | 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 |
| CN1869675A (en) * | 2006-06-27 | 2006-11-29 | 浙江大学 | Anti-interference metal/metal oxide pH electrode and preparation method |
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 |
| CN103698377A (en) | 2014-04-02 |
| CN103776880B (en) | 2015-10-21 |
| CN103472110A (en) | 2013-12-25 |
| CN103808780B (en) | 2015-11-04 |
| CN103472112B (en) | 2015-08-12 |
| CN103776885A (en) | 2014-05-07 |
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