CN103472107A - Silver/silver sulfite-based solid sulfite electrode and preparation method thereof - Google Patents

Silver/silver sulfite-based solid sulfite electrode and preparation method thereof Download PDF

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CN103472107A
CN103472107A CN2013104114685A CN201310411468A CN103472107A CN 103472107 A CN103472107 A CN 103472107A CN 2013104114685 A CN2013104114685 A CN 2013104114685A CN 201310411468 A CN201310411468 A CN 201310411468A CN 103472107 A CN103472107 A CN 103472107A
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silver
sulfite
electrode
photomask
filamentary
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CN103472107B (en
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叶瑛
贾健君
黄元凤
殷天雅
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 silver/silver sulfite-based solid sulfite electrode and a preparation method thereof. The silver/silver sulfite-based solid sulfite electrode comprises a silver wire, silver sulfite, a shading film and a heat-shrinkable tube, wherein a silver sulfite layer is electroplated on the lower surface of the silver wire in an in-situ mode; the shading film is coated on the external surface of the silver sulfite; and the heat-shrinkable tube is coated on the middle part of the silver wire and the upper part of the shading film. The silver/silver sulfite-based solid sulfite 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 sulfite ion content in seawater, culture water, industrial cycle cooling water and boiler water.

Description

A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof
Technical field
The present invention relates to a kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof.
Background technology
Sulphur is the modal chemical element of nature, is also food, chemical industry, pharmaceutical raw material commonly used.At nature, due to oxygen content difference in environment, sulphur can be different chemical combination states, comprises 6 valencys (sulfate radical), 4 valencys (inferior sulfate radical), 0 valency (sulphur) and-divalent (sulphion).Survey the distribution of different valence state sulphur in water body, for the understanding ecologic environment, micro-ecological environment is significant.
Summary of the invention
The purpose of this invention is to provide a kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof.
The objective of the invention is to be achieved through the following technical solutions:
Solid inferior sulfate radical electrode based on silver/silver sulfite comprises filamentary silver, silver sulfite, photomask, heat-shrink tube, filamentary silver lower surface original position is electroplated one deck silver sulfite, outside surface at silver sulfite coats one deck photomask, and the middle part of filamentary silver and the top of photomask are coated with heat-shrink tube.
It consists of described photomask by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
The preparation method's of the solid inferior sulfate radical electrode based on silver/silver sulfite step is as follows:
1) by diameter be 0.5 to 1 millimeter, the filamentary silver that length is 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with the solubility sulfite solution;
3) preparation photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
4) take filamentary silver as working electrode, i.e. anode, graphite is contrast electrode, the Pt sheet is auxiliary electrode, and negative electrode, be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 1 to 10 circulation, on the filamentary silver surface, forms silver sulfite, has electroplated rear water and has cleaned, and then with paper handkerchief, blots;
5) dip fast the photomask solution for preparing/outstanding mixed liquid by the filamentary silver part that is coated with silver sulfite, then be inverted and dry;
6) heat-shrink tube is coated on to the middle part of filamentary silver and the top of photomask, obtains solid inferior sulfate radical electrode.
Described diluted acid is one or several in the mass percent concentration hydrochloric acid that is 5% to 15%, sulfuric acid, nitric acid.
Described solubility sulphite is one or several of potassium sulfite, sodium sulphite, ammonium sulfite.
Solid inferior sulfate radical 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.This solid inferior sulfate radical electrode is applicable to survey the concentration of sulfite ion in the natural water areas such as ocean, lake, ocean current, and water environment is changed and carries out long-term on-line monitoring, and the discharge and the production run that also are applicable to industrial enterprise are carried out online observation.
the accompanying drawing explanation:
Fig. 1 is based on the structural representation of the solid inferior sulfate radical electrode of silver/silver sulfite;
In figure: filamentary silver 1, silver sulfite 2, photomask 3, heat-shrink tube 4.
Embodiment
Solid inferior sulfate radical electrode based on silver/silver sulfite comprises filamentary silver 1, silver sulfite 2, photomask 3, heat-shrink tube 4, filamentary silver 1 lower surface original position is electroplated one deck silver sulfite 2, outside surface at silver sulfite 2 coats one deck photomask 3, and the top of the middle part of filamentary silver 1 and photomask 3 is coated with heat-shrink tube 4.What described filamentary silver 1 needed coating silver sulfite and photomask is only the length of 1 centimetre of left and right as surveying an end, and remainder is as the conductor of signal transmission, without coating.
Filamentary silver 1 is the base material of electrode on the one hand, is also the conductor of response signal simultaneously.The silver sulfite 2 be coated on filamentary silver 1 plays a part the sulfite ion sensitive membrane, and the inferior sulfate radical of the dissolving in water body can form response electromotive force, i.e. voltage-type response signal between working electrode and contrast electrode.Because silver sulfite is shown in light and easily decomposes, outermost photomask plays a part to intercept light, and it also has water wettability and water tolerance concurrently.
It consists of described photomask by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.Wherein powdered carbon is light absorbent, uses the powdered carbon of nanometer to the sub-micron grade as far as possible, and as the acetylene powdered carbon, its particle mean size is usually at 0.1 to 0.5 micron.The dotriacontyl ammonio methacrylate belongs to quaternary ammonium compound, can improve the water wettability of film in formula, makes water soluble anion be easy to see through.Four (4-chlorphenyl) boric acid sylvite is film forming agent, and its formed film can allow negative ion to pass through, but stops kation to see through, so it has the cationic effect of shielding concurrently in formula.Because solvent volatility is stronger, photomask solution should be now with the current, do not store.
The preparation method's of the solid inferior sulfate radical electrode based on silver/silver sulfite step is as follows:
1) by diameter be 0.5 to 1 millimeter, the filamentary silver 1 that length is 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with the solubility sulfite solution;
3) preparation photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
4) take filamentary silver 1 as working electrode, i.e. anode, graphite is contrast electrode, the Pt sheet is auxiliary electrode, and negative electrode, be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 1 to 10 circulation, on filamentary silver 1 surface, forms silver sulfite 2, has electroplated rear water and has cleaned, and then with paper handkerchief, blots; Answer the gated sweep number of times, make the silver sulfite precipitation be unlikely to blocked up.Wipe away after dry and should apply as early as possible photomask, to avoid silver sulfite, see that light decomposes.
5) dip fast photomask 3 solution that prepare/outstanding mixed liquid by filamentary silver 1 part that is coated with silver sulfite 2, then be inverted and dry; Inversion is dried and is conducive to unnecessary coating solution and trickles towards rear portion along wire, avoids because the solution dump leaching makes film blocked up, causes response sensitivity to reduce.Photomask has light and the cationic effect of shielding of absorbing concurrently.
6) heat-shrink tube 4 is coated on to the middle part of filamentary silver 1 and the top of photomask 3, obtains solid inferior sulfate radical electrode.
Described diluted acid is one or several in the mass percent concentration hydrochloric acid that is 5% to 15%, sulfuric acid, nitric acid.Wipe oil also can be used other organic solvent, as gasoline.There is fine and close hard oxide film metal surface, and dilute acid pretreatment rear oxidation film is dissolved.While occurring in diluted acid when filamentary silver 1 bubbling, show that oxide film is dissolved, should take out and enter as early as possible next procedure from diluted acid, in order to avoid surface is by oxidation again.
Described solubility sulphite is one or several of potassium sulfite, sodium sulphite, ammonium sulfite.The easy oxidation of sulphite, solution should be now with the current, do not store.
Embodiment 1:
1) by diameter, be 0.5 millimeter, the filamentary silver 1 that length is 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) ammonium sulfite is dissolved in the water of 5 times, is mixed with ammonium sulfite solution;
3) preparation photomask 3 solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8%, dotriacontyl ammonio methacrylate 2 %, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 1%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 89%;
4) take filamentary silver 1 as working electrode (anode), graphite is contrast electrode, and the Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 5 circulations, on filamentary silver 1 surface, forms silver sulfite 2 precipitations; After plating completes, water cleans, and then with paper handkerchief, blots;
5) dip fast photomask 3 solution that prepare/outstanding mixed liquid by filamentary silver 1 part that is coated with silver sulfite 2, then be inverted and dry;
6) middle part that heat-shrink tube 4 is coated on to filamentary silver 1 does not have the part of silver sulfite 2 and the top of photomask 3, obtains solid inferior sulfate radical electrode.
Embodiment 2:
1) by diameter, be 0.8 millimeter, the filamentary silver 1 that length is 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 sulphite is dissolved in the water of 10 times, is mixed with sodium sulfite solution;
3) preparation photomask 3 solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 10%, dotriacontyl ammonio methacrylate 1 %, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 0.6%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 88.4%;
4) take filamentary silver 1 as working electrode (anode), graphite is contrast electrode, and the Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 10 circulations, on filamentary silver 1 surface, forms silver sulfite 2 precipitations; After plating completes, water cleans, and then with paper handkerchief, blots;
5) dip fast by filamentary silver 1 part that is coated with silver sulfite 2 photomask 3 solution that prepare, then be inverted and dry;
6) heat-shrink tube 4 is coated on to the middle part of filamentary silver 1 and the top of photomask 3, obtains solid inferior sulfate radical electrode.
Embodiment 3:
1) by diameter, be 0.8 millimeter, the filamentary silver 1 that length is 10 centimetres cleans successively in acetone and rare nitric acid, to remove surface and oil contaminant and oxide film, then with dry after washed with de-ionized water;
2) potassium sulfite is dissolved in the water of 8 times, is mixed with potassium sulfite solution;
3) preparation photomask 3 solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 9%, dotriacontyl ammonio methacrylate 1.6%, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 0.8%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 88.6%;
4) take filamentary silver 1 as working electrode (anode), graphite is contrast electrode, and the Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 1 circulation, on filamentary silver 1 surface, forms silver sulfite 2 precipitations; After plating completes, water cleans, and then with paper handkerchief, blots;
5) dip fast by filamentary silver 1 part that is coated with silver sulfite 2 photomask 3 solution that prepare, then be inverted and dry;
6) heat-shrink tube 4 is coated on to the middle part of filamentary silver 1 and the top of photomask 3, obtains solid inferior sulfate radical electrode.

Claims (5)

1. the solid inferior sulfate radical electrode based on silver/silver sulfite, it is characterized in that it comprises filamentary silver (1), silver sulfite (2), photomask (3), heat-shrink tube (4), filamentary silver (1) lower surface original position is electroplated one deck silver sulfite (2), outside surface at silver sulfite (2) coats one deck photomask (3), and the top of the middle part of filamentary silver (1) and photomask (3) is coated with heat-shrink tube (4).
2. a kind of solid inferior sulfate radical electrode based on silver/silver sulfite according to claim 1, it is characterized in that, described photomask is that it consists of by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
3. the preparation method of the solid inferior sulfate radical electrode based on silver/silver sulfite, is characterized in that, its step is as follows:
1) by diameter be 0.5 to 1 millimeter, the filamentary silver (1) that length is 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with the solubility sulfite solution;
3) preparation photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, dotriacontyl ammonio methacrylate 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%;
4) take filamentary silver (1) is working electrode, i.e. anode, and graphite is contrast electrode, the Pt sheet is auxiliary electrode, and negative electrode, be connected on electrochemical workstation, above-mentioned three electrodes are immersed in the solubility sulfite solution, adopt the scan round potential method, sweep speed is 30 to 80mVs -1, potential range 0, to 1V, scans 1 to 10 circulation, on filamentary silver (1) surface, forms silver sulfite (2), has electroplated rear water and has cleaned, and then with paper handkerchief, blots;
5) dip fast photomask (3) solution for preparing/outstanding mixed liquid by filamentary silver (1) part that is coated with silver sulfite (2), then be inverted and dry;
6) heat-shrink tube (4) is coated on to the middle part of filamentary silver (1) and the top of photomask (3), obtains solid inferior sulfate radical electrode.
4. the preparation method of a kind of solid inferior sulfate radical electrode based on silver/silver sulfite according to claim 3, is characterized in that, described diluted acid is one or several in the mass percent concentration hydrochloric acid that is 5% to 15%, sulfuric acid, nitric acid.
5. the preparation method of a kind of solid inferior sulfate radical electrode based on silver/silver sulfite according to claim 3, is characterized in that, described solubility sulphite is one or several of potassium sulfite, sodium sulphite, ammonium sulfite.
CN201310411468.5A 2013-03-28 2013-09-11 A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof Expired - Fee Related CN103472107B (en)

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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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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
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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
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
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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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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