CN103472107B - A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof - Google Patents
A kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof.It comprises filamentary silver, silver sulfite, photomask, heat-shrink tube, and filamentary silver lower surface original position electroplates one deck silver sulfite, and at the coated one deck photomask of the outside surface of silver sulfite, the middle part of filamentary silver and the top of photomask are coated with heat-shrink tube.It is high that the present invention has physical strength, toughness is large, highly sensitive, volume is little, probe response is fast, and Monitoring lower-cut is extremely low, the advantages such as long service life, it and solid reference electrode support the use, and are applicable to carry out on-line water flushing and long-term in-situ monitoring to the sulfite ion content in seawater, breeding water, industrial circulating cooling water and boiler water.
Description
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 conventional food, chemical industry, pharmaceutical raw material.At nature, because oxygen content in environment is different, sulphur in different chemical combination states, can comprise 6 valencys (sulfate radical), 4 valencys (inferior sulfate radical), 0 valency (sulphur) and-divalent (sulphion).The distribution of different valence state sulphur in detection water body, for understanding ecologic environment, micro-ecological environment is significant.
Summary of the invention
The object of this invention is to provide a kind of solid inferior sulfate radical electrode based on silver/silver sulfite and preparation method thereof.
The object 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 electroplates one deck silver sulfite, at the coated one deck photomask of the outside surface of silver sulfite, 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%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
Step based on the preparation method of the solid inferior sulfate radical electrode of silver/silver sulfite 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with solubility sulfite solution;
3) prepare photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, tridodecylmethylammonium ammonium chloride 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, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, be immersed in solubility sulfite 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 silver sulfite on filamentary silver surface, has electroplated the cleaning of rear water, has then blotted with paper handkerchief;
5) dip the photomask solution/outstanding mixed liquid prepared by the filamentary silver part being coated with silver sulfite fast, be then inverted and dry;
6) heat-shrink tube is coated on the middle part of filamentary silver and the top of photomask, namely obtains solid inferior sulfate radical electrode.
Described diluted acid to be mass percent concentration be 5% to 15% hydrochloric acid, sulfuric acid, one or several in nitric acid.
Described solubility sulphite be potassium sulfite, sodium sulphite, ammonium sulfite one or several.
Solid inferior sulfate radical 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 inferior sulfate radical electrode is applicable to the concentration detecting sulfite 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 of the solid inferior sulfate radical electrode based on 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 electroplates one deck silver sulfite 2, at the coated one deck photomask 3 of the outside surface of silver sulfite 2, the middle part of filamentary silver 1 and the top of photomask 3 are coated with heat-shrink tube 4.Described filamentary silver 1 needs the length be only as 1 cm detecting one end of coated silver sulfite and photomask, and remainder is used as the conductor of signal transmission, without the need to coated.
Filamentary silver 1 one aspect is the base material of electrode, is also the conductor of response signal simultaneously.The silver sulfite 2 be coated on filamentary silver 1 plays a part 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 that light 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%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.Wherein powdered carbon is light absorbent, and use nanometer to the powdered carbon of sub-micron grade, as acetylene powdered carbon, its particle mean size is usually at 0.1 to 0.5 micron as far as possible.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 is film forming agent, and the film that it is formed can allow negative ion to pass through, but stops cation permeable, and therefore it has the cationic effect of shielding concurrently in formula.Because solvent volatility is comparatively strong, photomask solution should be now with the current, do not store.
Step based on the preparation method of the solid inferior sulfate radical electrode of silver/silver sulfite 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with solubility sulfite solution;
3) prepare photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
4) with filamentary silver 1 for working electrode, i.e. anode, graphite is contrast electrode, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, be immersed in solubility sulfite 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 silver sulfite 2 on filamentary silver 1 surface, has electroplated the cleaning of rear water, has then blotted with paper handkerchief; Answer gated sweep number of times, silver sulfite is precipitated and is unlikely to blocked up.Wipe after doing and should apply photomask as early as possible, see that to avoid silver sulfite light decomposes.
5) dip the photomask 3 solution/outstanding mixed liquid prepared by filamentary silver 1 part being coated with silver sulfite 2 fast, be then inverted and dry; Be inverted to dry and be conducive to unnecessary coating solution and trickle towards rear portion along wire, avoid, because solution dump leaching makes film blocked up, causing response sensitivity to reduce.Photomask has concurrently and absorbs light and the cationic effect of shielding.
6) heat-shrink tube 4 is coated on the middle part of filamentary silver 1 and the top of photomask 3, namely obtains solid inferior sulfate radical 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 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.
Described solubility sulphite be potassium sulfite, sodium sulphite, ammonium sulfite one or several.Sulphite is oxidizable, and solution should be now with the current, do not store.
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) ammonium sulfite is dissolved in the water of 5 times, is mixed with ammonium sulfite solution;
3) photomask 3 solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: powdered carbon 8%, tridodecylmethylammonium ammonium chloride 2 %, four (4-chlorphenyl) boric acid sylvite (potassium tetrakis (4-chlorophenyl) borate) 1%, tetrahydrofuran (THF) or dimethyl formamide (DMF) 89%;
4) with filamentary silver 1 for working electrode (anode), graphite is contrast electrode, and Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, be immersed in solubility sulfite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 5 circulations, forms silver sulfite 2 precipitate on filamentary silver 1 surface; Electroplate the cleaning of rear water, then blotted with paper handkerchief;
5) dip the photomask 3 solution/outstanding mixed liquid prepared by filamentary silver 1 part being coated with silver sulfite 2 fast, be then inverted and dry;
6) middle part heat-shrink tube 4 being coated on filamentary silver 1 does not have the part of silver sulfite 2 and the top of photomask 3, namely obtains solid inferior sulfate radical electrode.
Embodiment 2:
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) sodium sulphite is dissolved in the water of 10 times, is mixed with sodium sulfite solution;
3) photomask 3 solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: powdered carbon 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%;
4) with filamentary silver 1 for working electrode (anode), graphite is contrast electrode, and Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, be immersed in solubility sulfite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80mVs
-1, potential range 0 to 1V, scans 10 circulations, forms silver sulfite 2 precipitate on filamentary silver 1 surface; Electroplate the cleaning of rear water, then blotted with paper handkerchief;
5) dip photomask 3 solution prepared by filamentary silver 1 part being coated with silver sulfite 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the middle part of filamentary silver 1 and the top of photomask 3, namely obtains solid inferior sulfate radical 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 dust technology, 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) photomask 3 solution/outstanding mixed liquid is prepared, it consists of by percentage to the quality: powdered carbon 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%;
4) with filamentary silver 1 for working electrode (anode), graphite is contrast electrode, and Pt sheet is auxiliary electrode (negative electrode), be connected on electrochemical workstation, be immersed in solubility sulfite 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 circulation, forms silver sulfite 2 precipitate on filamentary silver 1 surface; Electroplate the cleaning of rear water, then blotted with paper handkerchief;
5) dip photomask 3 solution prepared by filamentary silver 1 part being coated with silver sulfite 2 fast, be then inverted and dry;
6) heat-shrink tube 4 is coated on the middle part of filamentary silver 1 and the top of photomask 3, namely obtains solid inferior sulfate radical electrode.
Claims (4)
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 electroplates one deck silver sulfite (2), the coated one deck photomask (3) of the outside surface of silver sulfite (2), the middle part of filamentary silver (1) and the top of photomask (3) are coated with heat-shrink tube (4); It consists of described photomask (3) by percentage to the quality: powdered carbon 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%.
2., based on a preparation method for the solid inferior sulfate radical electrode of silver/silver sulfite, it is characterized in that, its step 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) solubility sulphite is dissolved in the water of 5 to 10 times, is mixed with solubility sulfite solution;
3) prepare photomask solution/outstanding mixed liquid, it consists of by percentage to the quality: powdered carbon 8-10%, tridodecylmethylammonium ammonium chloride 1-2%, four (4-chlorphenyl) boric acid sylvite 0.6-1%, tetrahydrofuran or dimethyl formamide 87-90%;
4) with filamentary silver (1) for working electrode, i.e. anode, graphite is contrast electrode, Pt sheet is auxiliary electrode, i.e. negative electrode, is connected on electrochemical workstation, be immersed in solubility sulfite solution by above-mentioned three electrodes, adopt scan round potential method, sweep speed is 30 to 80 mVs
-1, potential range 0 to 1V, scans 1 to 10 circulation, forms silver sulfite (2) on filamentary silver (1) surface, has electroplated the cleaning of rear water, has then blotted with paper handkerchief;
5) dip photomask (3) solution/outstanding mixed liquid prepared by filamentary silver (1) part being coated with silver sulfite (2) fast, be then inverted and dry;
6) heat-shrink tube (4) is coated on the middle part of filamentary silver (1) and the top of photomask (3), namely obtains solid inferior sulfate radical electrode.
3. the preparation method of a kind of solid inferior sulfate radical electrode based on silver/silver sulfite according to claim 2, 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.
4. the preparation method of a kind of solid inferior sulfate radical electrode based on silver/silver sulfite according to claim 2, is characterized in that, described solubility sulphite be potassium sulfite, sodium sulphite, ammonium sulfite one or several.
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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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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 |
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CN201310410960.0A Expired - Fee Related CN103472106B (en) | 2013-03-28 | 2013-09-11 | Lead silicate solid electrode using silver as base material and preparation method thereof |
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 |
CN201310410948.XA Expired - Fee Related CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
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CN103472113B (en) | 2015-08-12 |
CN103698379A (en) | 2014-04-02 |
CN103472105B (en) | 2015-08-12 |
CN103472104B (en) | 2015-06-17 |
CN103472106A (en) | 2013-12-25 |
CN103808780A (en) | 2014-05-21 |
CN103472110A (en) | 2013-12-25 |
CN103472110B (en) | 2015-06-17 |
CN103196971A (en) | 2013-07-10 |
CN103472111A (en) | 2013-12-25 |
CN103472112B (en) | 2015-08-12 |
CN103776885A (en) | 2014-05-07 |
CN103776880A (en) | 2014-05-07 |
CN103472106B (en) | 2015-02-25 |
CN103675068B (en) | 2015-10-21 |
CN103675068A (en) | 2014-03-26 |
CN103472112A (en) | 2013-12-25 |
CN103698377B (en) | 2016-05-18 |
CN103698377A (en) | 2014-04-02 |
CN103808780B (en) | 2015-11-04 |
CN103472107A (en) | 2013-12-25 |
CN103472109A (en) | 2013-12-25 |
CN103776885B (en) | 2015-12-09 |
CN103472113A (en) | 2013-12-25 |
CN103698379B (en) | 2015-08-12 |
CN103472111B (en) | 2015-06-17 |
CN103472109B (en) | 2015-06-17 |
CN103472104A (en) | 2013-12-25 |
CN103776880B (en) | 2015-10-21 |
CN103472105A (en) | 2013-12-25 |
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