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 PDF

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CN103472106B
CN103472106B CN201310410960.0A CN201310410960A CN103472106B CN 103472106 B CN103472106 B CN 103472106B CN 201310410960 A CN201310410960 A CN 201310410960A CN 103472106 B CN103472106 B CN 103472106B
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CN103472106A (en
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叶瑛
贾健君
黄元凤
殷天雅
阎康康
秦华伟
张斌
潘依雯
陈雪刚
夏枚生
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Zhejiang University ZJU
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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

A kind of take silver as lead silicate solid electrode of base material and preparation method thereof
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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CN 201310104390 Withdrawn CN103196971A (en) 2013-03-28 2013-03-28 Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate
CN201310411530.0A Expired - Fee Related CN103472112B (en) 2013-03-28 2013-09-11 A kind of solid phosphoric acid root electrode based on silver/metal phosphate and preparation method thereof
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CN 201310104390 Withdrawn CN103196971A (en) 2013-03-28 2013-03-28 Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate
CN201310411530.0A Expired - Fee Related CN103472112B (en) 2013-03-28 2013-09-11 A kind of solid phosphoric acid root electrode based on silver/metal phosphate and preparation method thereof
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CN201310411531.5A Expired - Fee Related CN103472113B (en) 2013-03-28 2013-09-11 Based on the solid carbon acid group electrode and preparation method thereof of rare earth/rare earth carbonate
CN201310410930.XA Expired - Fee Related CN103472109B (en) 2013-03-28 2013-09-11 Arsenite solid electrode using metal wire as base material and preparation method thereof
CN201310410956.4A Expired - Fee Related CN103472110B (en) 2013-03-28 2013-09-11 Arsenate solid electrode using metal wire as base material and preparation method thereof
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

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CN201310482283.3A Expired - Fee Related CN103698377B (en) 2013-03-28 2013-10-16 A kind of preparation method of metal/metal hydroxide pH electrode
CN201310698042.2A Expired - Fee Related CN103698379B (en) 2013-03-28 2013-12-19 A kind of solid ammonium ion electrode based on ammonium magnesium phosphate and preparation method thereof
CN201310698146.3A Expired - Fee Related CN103675068B (en) 2013-03-28 2013-12-19 A kind of solid nitric acid root electrode based on nitric acid oxidation bismuth and preparation method thereof
CN201410019461.3A Expired - Fee Related CN103776880B (en) 2013-03-28 2014-01-16 A kind of with titanium silk solid reference electrode that is base material and preparation method thereof
CN201410019466.6A Expired - Fee Related CN103776885B (en) 2013-03-28 2014-01-16 A kind of take tinsel as silicate electrode of base material and preparation method thereof
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