CN103776885B - A kind of take tinsel as silicate electrode of base material and preparation method thereof - Google Patents
A kind of take tinsel as silicate electrode of base material and preparation method thereof Download PDFInfo
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- CN103776885B CN103776885B CN201410019466.6A CN201410019466A CN103776885B CN 103776885 B CN103776885 B CN 103776885B CN 201410019466 A CN201410019466 A CN 201410019466A CN 103776885 B CN103776885 B CN 103776885B
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title abstract 2
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 4
- 229910052745 lead Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 10
- 238000007654 immersion Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 9
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- -1 silicate ion Chemical class 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000013535 sea water Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000012736 aqueous medium Substances 0.000 abstract 1
- 238000009395 breeding Methods 0.000 abstract 1
- 230000001488 breeding effect Effects 0.000 abstract 1
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 6
- 239000000470 constituent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910015868 MSiO Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Inert Electrodes (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Metals (AREA)
- Hybrid Cells (AREA)
- Luminescent Compositions (AREA)
- Chemically Coating (AREA)
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
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Abstract
The invention discloses a kind of take tinsel as silicate electrode of base material and preparation method thereof.It comprises tinsel, metal silicate layer, perfluorinated sulfonic resin diaphragm and heat-shrink tube; at tinsel bottom clad metal silicate layer; the coated perfluorinated sulfonic resin diaphragm of metal silicate layer, is coated with heat-shrink tube with perfluorinated sulfonic resin diaphragm top in the middle part of tinsel.Described tinsel is Zr, Hf, Co, Ni, Pb or Zn.It is little that the present invention has volume, toughness is large, physical strength is high, highly sensitive, and probe response is fast, signal stabilization is good, Monitoring lower-cut is extremely low, the advantages such as long service life, and it and solid reference electrode support the use, be applicable to seawater, Inland Water, breeding water, underground water and spring, and chemistry, silicate ion content in chemical industry aqueous medium carry out on-line water flushing and long-term in-situ monitoring.
Description
Technical field
The present invention relates to a kind of take tinsel as silicate 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 the invention is to overcome the deficiencies in the prior art, providing a kind of take tinsel as silicate electrode of base material and preparation method thereof.
Be that the silicate electrode of base material comprises tinsel, metal silicate layer, perfluorinated sulfonic resin diaphragm and heat-shrink tube with tinsel; at tinsel bottom clad metal silicate layer; the coated perfluorinated sulfonic resin diaphragm of metal silicate layer, is coated with heat-shrink tube with perfluorinated sulfonic resin diaphragm top in the middle part of tinsel.
Described tinsel (1) is Zr, Hf, Co, Ni, Pb or Zn.
The preparation method's step taking tinsel as the silicate electrode of base material is as follows:
1) take 1 mass parts metasilicic acid, 3 to 5 mass parts silicon carbide powders, add gross mass 5 to 8 times of water, stir into uniform suspending liquid;
2) tinsel is cut into the length of 5 to 15 centimetres, ultrasound wave process 2 to 5 minutes in suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 0.5 to 1.5V, using tinsel as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, tinsel bottom as working electrode is immersed in scanning 2 to 10 sections in suspending liquid, generates metal silicate layer in tinsel lower surface;
4) generation has the tinsel of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.5% to 1%, taking out after inversion is dried repeats once, then aging 12 to 24 hours of constant temperature in 60 to 80 ° of C baking ovens, at metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm wiry;
5) heat-shrink tube is coated on the top of middle part wiry and perfluorinated sulfonic resin diaphragm, namely obtaining with tinsel is the silicate electrode of base material.
Described metasilicic acid is commercial metasilicic acid powder, or in sodium silicate solution dust technology or watery hydrochloric acid and the metasilicic acid gel of preparation.
Solid metal silicate 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 metal silicate 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 explanation
Fig. 1 is the structural representation of the silicate electrode taking tinsel as base material.
Embodiment
Be that the silicate electrode of base material comprises tinsel 1, metal silicate layer 2, perfluorinated sulfonic resin diaphragm 3 and heat-shrink tube 4 with tinsel; at tinsel 1 bottom clad metal silicate layer 2; the coated perfluorinated sulfonic resin diaphragm 3 of metal silicate layer 2, is coated with heat-shrink tube 4 with perfluorinated sulfonic resin diaphragm 3 top in the middle part of tinsel 1.
Described tinsel 1 is Zr, Hf, Co, Ni, Pb or Zn.Described tinsel 1 needs clad nano metal and metal silicate 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 tinsel 1 as base material, be because it has good conductivity and toughness, and metal silicate 2 has relatively high conductivity, its electrochemical properties is better than other silicate.This electrode is using tinsel 1 as base material, and metal silicate 2 is sensitive membrane, has taken into account two kinds of materials advantage separately.
Tinsel 1 one aspect is the base material of electrode, is also the conductor of response signal simultaneously.The metal silicate 2 formed through electrochemical reaction 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 metal silicate 2 electrode.
The preparation method's step taking tinsel as the silicate electrode of base material is as follows:
1) take 1 mass parts metasilicic acid, 3 to 5 mass parts silicon carbide powders, add gross mass 5 to 8 times of water, stir into uniform suspending liquid;
Metasilicic acid makes solution keep sour environment, and provides silicate for subsequent reactions.Suggestion prepares metasilicic acid by chemical reaction from sodium silicate, as:
Na
2SiO
3+2HNO
3=H
2SiO
3+2NaNO
3
Gained metasilicic acid is gelatinous precipitate, centrifugal, can use after drip washing.Suggestion first with dust technology or watery hydrochloric acid, then is cleaned with water.Compare with commercial product, homemade metasilicic acid gel does not live through dehydration and drying, has higher chemical activity.Institute's water content in metasilicic acid can be ignored, because its solubleness in water is lower when weighing.
Silit in suspending liquid has very high hardness, plays a part abrasive material, is also antioxidant on the other hand, tinsel 1 surface can be suppressed to be reoxidized.
2) tinsel 1 is cut into the length of 5 to 15 centimetres, ultrasound wave process 2 to 5 minutes in suspending liquid, removing surface film oxide;
Under hyperacoustic effect, the shock on silicon carbide powder and tinsel 1 surface forms strong mechanical friction, thus removes surface oxide layer, the phlogistication of silit, and acid condition inhibits the generation of oxide, oxyhydroxide.
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 0.5 to 1.5V, using tinsel 1 as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, tinsel bottom as working electrode is immersed in scanning 2 to 10 sections in suspending liquid, generates metal silicate layer 2 in tinsel lower surface;
In cyclic voltammetry scanning process, tinsel 1 surface is reacted with the silicate in suspending liquid:
M+H
2SiO
3=MSiO
3+H
2（2）
M in formula is metal or metal cation.
4) coated diaphragm 3.Electrode first cleans with water; clean with anhydrous alcohol again; drying rear immersion concentration is in the perfluor sulfoacid resin solution of 0.5% to 1%; taking out after inversion is dried repeats once; then aging 12 to 24 hours of constant temperature in 60 to 80 ° of C baking ovens, namely at electrode surface coated one deck perfluorinated sulfonic resin diaphragm 3.
Perfluorinated sulfonic resin is the product of du pont company, and English trade name is Nafion.Its film that formed has microcellular structure, can allow proton, conductive ions passes through, and can shield other harmful constituent to the corrosion of electrode sensitive film and injury simultaneously, shield.
4) generation has the tinsel of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.5% to 1%, taking out after inversion is dried repeats once, then aging 12 to 24 hours of constant temperature in 60 to 80 ° of C baking ovens, at metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 wiry;
Perfluorinated sulfonic resin is the product of du pont company, and English trade name is Nafion.Its film that formed has microcellular structure, can allow proton, conductive ions passes through, and can shield other harmful constituent to the corrosion of electrode sensitive film and injury simultaneously, shield.
5) heat-shrink tube 4 is coated on the middle part of tinsel 1 and the top of perfluorinated sulfonic resin diaphragm 3, namely obtaining with tinsel is the silicate electrode of base material.Heat-shrink tube 4 insulation and protective effect.
Described metasilicic acid is commercial metasilicic acid powder, or in sodium silicate solution dust technology or watery hydrochloric acid and the metasilicic acid gel of preparation.
Embodiment 1:
1) take 10 grams of metasilicic acids, 30 grams of silicon carbide powders, add 200 grams of water, stir into uniform suspending liquid; Described metasilicic acid is commercial metasilicic acid powder;
2) Zr silk is cut into the length of 5 centimetres, ultrasound wave process 5 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 0.5V, using Zr silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, tinsel bottom as working electrode is immersed in scanning 10 sections in suspending liquid, generates metal silicate layer 2 in tinsel lower surface;
4) generation has the Zr silk of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.5%, taking out after inversion is dried repeats once, then aging 24 hours of constant temperature in 60 ° of C baking ovens, at the metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 of Zr silk;
5) heat-shrink tube (4) is coated on the middle part of Zr silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Zr silk be base material.
Embodiment 2:
1) take 5 grams of metasilicic acids, 20 grams of silicon carbide powders, add 150 grams of water, stir into uniform suspending liquid; Described metasilicic acid is commercial metasilicic acid powder;
2) Hf silk 1 is cut into the length of 10 centimetres, ultrasound wave process 4 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 1V, using Hf silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, tinsel bottom as working electrode is immersed in scanning 6 sections in suspending liquid, generates metal silicate layer 2 in Hf silk lower surface;
4) generation has the tinsel of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.8%8, taking out after inversion is dried repeats once, then aging 18 hours of constant temperature in 70 ° of C baking ovens, at the metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 of Hf silk;
5) heat-shrink tube 4 is coated on the middle part of Hf silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Hf silk be base material.
Embodiment 3:
1) take 5 grams of metasilicic acids, 25 grams of silicon carbide powders, add 240 grams of water, stir into uniform suspending liquid; Described metasilicic acid is in sodium silicate solution dust technology or watery hydrochloric acid and the metasilicic acid gel of preparation;
2) Pb silk 1 is cut into the length of 15 centimetres, ultrasound wave process 2 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 1.5V, using Pb silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, Pb silk bottom as working electrode is immersed in scanning 2 to 10 sections in suspending liquid, generates metal silicate layer 2 in Pb silk lower surface;
4) generation has the Pb silk of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 1%, taking out after inversion is dried repeats once, then aging 12 hours of constant temperature in 80 ° of C baking ovens, at metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm (3) of Pb silk;
5) heat-shrink tube 4 is coated on the middle part of Pb silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Pb silk be base material.
Embodiment 4:
1) take 10 grams of metasilicic acids, 30 grams of silicon carbide powders, add 200 grams of water, stir into uniform suspending liquid; Described metasilicic acid is commercial metasilicic acid powder;
2) Co silk 1 is cut into the length of 5 centimetres, ultrasound wave process 3 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 0.8V, using Co silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, Co silk bottom as working electrode is immersed in scanning 4 sections in suspending liquid, generates metal silicate layer 2 in Co silk lower surface;
4) generation has the tinsel of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.5%, taking out after inversion is dried repeats once, then aging 24 hours of constant temperature in 60 ° of C baking ovens, at the metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 of Co silk;
5) heat-shrink tube 4 is coated on the middle part of Co silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Co silk be base material.
Embodiment 5:
1) take 5 grams of metasilicic acids, 20 grams of silicon carbide powders, add 150 grams of water, stir into uniform suspending liquid; Described metasilicic acid is in sodium silicate solution dust technology or watery hydrochloric acid and the metasilicic acid gel of preparation;
2) Ni silk 1 is cut into the length of 10 centimetres, ultrasound wave process 4 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 1.2V, using Ni silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, Ni silk bottom as working electrode is immersed in scanning 6 sections in suspending liquid, generates metal silicate layer (2) in Ni silk lower surface;
4) generation has the Ni silk of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.8%8, taking out after inversion is dried repeats once, then aging 18 hours of constant temperature in 70 ° of C baking ovens, at the metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 of Ni silk;
5) heat-shrink tube 4 is coated on the middle part of Ni silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Ni silk be base material.
Embodiment 6:
1) take 5 grams of metasilicic acids, 25 grams of silicon carbide powders, add 240 grams of water, stir into uniform suspending liquid;
2) Zn silk 1 is cut into the length of 12 centimetres, ultrasound wave process 2 minutes in above suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 1.1V, using Zn silk as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, Zn silk bottom as working electrode is immersed in scanning 2 sections in suspending liquid, generates metal silicate layer 2 in Zn silk lower surface;
4) generation has the Zn silk of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 1%, taking out after inversion is dried repeats once, then aging 12 hours of constant temperature in 80 ° of C baking ovens, at the metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm 3 of Zn silk;
5) heat-shrink tube 4 is coated on the middle part of Zn silk and the top of perfluorinated sulfonic resin diaphragm 3, the silicate electrode that namely to obtain with Zn silk be base material.
Claims (3)
1. be a preparation method for the silicate electrode of base material with tinsel, it is characterized in that, its step is as follows:
1) take 1 mass parts metasilicic acid, 3 to 5 mass parts silicon carbide powders, add gross mass 5 to 8 times of water, stir into uniform suspending liquid;
2) tinsel (1) is cut into the length of 5 to 15 centimetres, ultrasound wave process 2 to 5 minutes in suspending liquid, removing surface film oxide;
3) CHI760D electrochemical workstation is regulated, the scanning voltage upper limit is set to 0.5 to 1.5V, using tinsel (1) as working electrode, platinum electrode is auxiliary electrode, business Ag/AgCl electrode is contrast electrode, tinsel bottom as working electrode is immersed in scanning 2 to 10 sections in suspending liquid, generates metal silicate layer (2) in tinsel lower surface;
4) generation has the tinsel of metal silicate first to clean with water, clean with anhydrous alcohol again, drying rear immersion mass percentage concentration is in the perfluor sulfoacid resin solution of 0.5% to 1%, taking out after inversion is dried repeats once, then aging 12 to 24 hours of constant temperature in 60 to 80 ° of C baking ovens, metal silicate layer Surface coating perfluorinated sulfonic resin diaphragm (3) wiry;
5) heat-shrink tube (4) is coated on the middle part of tinsel (1) and the top of perfluorinated sulfonic resin diaphragm (3), namely obtaining with tinsel is the silicate electrode of base material;
Described is that the silicate electrode of base material comprises tinsel (1), metal silicate layer (2), perfluorinated sulfonic resin diaphragm (3) and heat-shrink tube (4) with tinsel; in tinsel (1) bottom clad metal silicate layer (2); the coated perfluorinated sulfonic resin diaphragm (3) of metal silicate layer (2), is coated with heat-shrink tube (4) at tinsel (1) middle part and perfluorinated sulfonic resin diaphragm (3) top.
2. according to claim 1 a kind of take tinsel as the preparation method of the silicate electrode of base material, it is characterized in that, described tinsel (1) is Zr, Hf, Co, Ni, Pb or Zn.
3. according to claim 1 a kind of take tinsel as the preparation method of the silicate electrode of base material, it is characterized in that, described metasilicic acid is commercial metasilicic acid powder, or in sodium silicate solution dust technology or watery hydrochloric acid and the metasilicic acid gel of preparation.
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|---|---|---|---|
| CN201410019466.6A 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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|---|---|---|---|
| CN201310104390.2 | 2013-03-28 | ||
| CN 201310104390 CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| CN201410019466.6A 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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|---|---|
| CN103776885A CN103776885A (en) | 2014-05-07 |
| CN103776885B true CN103776885B (en) | 2015-12-09 |
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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 |
| 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 |
| 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 |
| CN201310410948.XA Expired - Fee Related CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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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| CN 201310104390 Withdrawn CN103196971A (en) | 2013-03-28 | 2013-03-28 | Preparation method of solid phosphate ion electrode based on aluminum and aluminum phosphate |
| 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 |
| 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 |
| CN201310410948.XA Expired - Fee Related CN103472104B (en) | 2013-03-28 | 2013-09-11 | Silver/barium sulfate-based solid sulfate electrode and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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| 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 |
| 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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| US11977047B2 (en) * | 2020-08-28 | 2024-05-07 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Silver-silver sulfide reference electrode |
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Also Published As
| Publication number | Publication date |
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| CN103776880A (en) | 2014-05-07 |
| CN103472107A (en) | 2013-12-25 |
| CN103698377B (en) | 2016-05-18 |
| CN103675068A (en) | 2014-03-26 |
| CN103472104A (en) | 2013-12-25 |
| CN103808780A (en) | 2014-05-21 |
| CN103776880B (en) | 2015-10-21 |
| CN103196971A (en) | 2013-07-10 |
| CN103472111A (en) | 2013-12-25 |
| CN103472113B (en) | 2015-08-12 |
| CN103808780B (en) | 2015-11-04 |
| CN103698379A (en) | 2014-04-02 |
| CN103472104B (en) | 2015-06-17 |
| CN103472113A (en) | 2013-12-25 |
| CN103472109A (en) | 2013-12-25 |
| CN103698377A (en) | 2014-04-02 |
| CN103675068B (en) | 2015-10-21 |
| CN103472109B (en) | 2015-06-17 |
| CN103472106B (en) | 2015-02-25 |
| CN103472112A (en) | 2013-12-25 |
| CN103472112B (en) | 2015-08-12 |
| CN103776885A (en) | 2014-05-07 |
| CN103698379B (en) | 2015-08-12 |
| CN103472106A (en) | 2013-12-25 |
| CN103472110B (en) | 2015-06-17 |
| CN103472105B (en) | 2015-08-12 |
| CN103472107B (en) | 2015-08-12 |
| CN103472110A (en) | 2013-12-25 |
| CN103472111B (en) | 2015-06-17 |
| CN103472105A (en) | 2013-12-25 |
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